Polyurethane/urea compositions

ABSTRACT

A valve in the form of a medical device, article, or implant that is composed wholly or partly of a biomaterial, the biomaterial comprising a polyurethane or polyurethane urea elastomeric composition having a plurality of soft segments and hard segments, such that the plurality of soft segments are each derived from at least one block copolymer segment of Formula 1 and optionally an additional polyol or polyamine. The valve may include a plurality of 
     
       
         
         
             
             
         
       
     
     valve leaflets and a support structure with one or more of the valve leaflets being composed wholly or partly of the biomaterial.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. patent applicationSer. No. 15/150,737, filed May 10, 2016, now U.S. Pat. No. 10,266,657,which claims priority from Australian Provisional Patent Application No.2015904428, filed on 29 Oct. 2015, the entire contents of each of whichare incorporated herein by reference in their entireties.

FIELD

The present disclosure relates to soft block copolymer segments for athermoplastic polyurethane or polyurethaneurea elastomer composition andtheir reaction products with divalent compounds, such as diisocyanates,chain extenders and optional additional polyols or polyamines. Alsodisclosed are methods for the preparation of the soft block copolymersegments and reaction products, and the use of these components in themanufacture of materials such as biomaterials for devices, articles orimplants.

BACKGROUND

The statements in this section merely provide background informationrelated to the present disclosure and may not constitute prior art.

Previously, polyurethanes based on two or more macrodiols which arechemically different have been reported. This has been achieved by usinga mixture or a blend of the macrodiols for making the polyurethane, andemploying either a one-step or a two-step polymerisation procedure. Thisapproach has a number of disadvantages including: in most cases, if themacrodiols are not miscible, the resulting polyurethane iscompositionally heterogeneous; only a limited number of macrodiolcombinations can be used to make polyurethanes with good mechanicalproperties, and the segments from each of the macrodiols are randomlydistributed within the polyurethane chain (often resulting inpolyurethanes with poor mechanical properties); and the incorporation ofhigher molecular weight macrodiols or macrodiamines are limited topolyols such as polyether, polyester or polycarbonates.

There is a need for identifying alternative block copolymers for use inpolyurethane or polyurethaneurea elastomer compositions for preparingvarious polymer products with a broad range of mechanical properties.The alternative block copolymers may address one or more disadvantagesof previous approaches.

Any discussion of documents, acts, materials, devices, articles or thelike which has been included in the present specification is not to betaken as an admission that any or all of these matters form part of theprior art base or were common general knowledge in the field relevant tothe present disclosure as it existed before the priority date of eachclaim of this application.

SUMMARY

The present disclosure relates to macrodiols and macrodiamines which arechemically linked (linked-macrodiols or macrodiamines) to contain one ormore chemically distinct moieties within a polymeric backbone. The saidmacrodiols and macrodiamines are useful in formulatingpolyurethanes/ureas for biomedical and non-biomedical applications.

In a first aspect, there is provided a block copolymer segment ofFormula 1 for a thermoplastic polyurethane or polyurethaneurea elastomercomposition:

wherein

A¹ is an endcapping group;

A² is hydrogen or an endcapping group;

each Y¹ and Y² are independently selected from a polysiloxane macrodiol,polysiloxane macrodiamine, polyether macrodiol, polycarbonate macrodiol,polyester macrodiol, and a polyhydrocarbon macrodiol;

each L¹ and L² is a divalent linking group independently selected fromurethane, urea carbonate, amide, ester, and phosphonate;

n is an integer of 1 to 5;

t is an integer of 0 to 5; and

Q is selected from a moiety according to:

-   -   wherein    -   R¹, R², R³, and R⁴, are each independently selected from        hydrogen and an optionally substituted straight chain, branched        or cyclic, saturated and unsaturated hydrocarbon radical;    -   R⁵ and R⁶ are each independently selected from a straight chain,        branched or cyclic, saturated and unsaturated hydrocarbon        radical optionally interrupted with one or more heteroatoms        independently selected from O, N and S;    -   m is an integer of 1 to 50;    -   X is a group selected from OC(O)O, C(O)O and O;    -   q is an integer of 1 to 50; and r is an integer of 2 to 50.

In a second aspect, there is provided a thermoplastic polyurethane orpolyurethaneurea elastomer composition comprising a plurality of softsegments and hard segments, wherein the plurality of soft segments areeach derived from at least one block copolymer segment of Formula 1according to the first aspect above, or any embodiments thereofdescribed herein, and optionally an additional polyol or polyamine.

In a third aspect, there is provided a thermoplastic polyurethane orpolyurethaneurea elastomer composition comprising a reaction product of:

-   -   i. at least one block copolymer segment of Formula 1 according        to the first aspect above, or any embodiments thereof described        herein;    -   ii. a diisocyanate;    -   iii. one or more chain extenders; and    -   iv. optionally an additional polyol or polyamine.

In a fourth aspect, there is provided a material comprising athermoplastic polyurethane or polyurethaneurea elastomeric compositionaccording to the above second or third aspect, or any embodimentsthereof described herein.

In a fifth aspect, there is provided a device or article which iscomposed wholly or partly of the polyurethane or polyurethaneureaelastomeric composition according to the above second or third aspect,or any embodiments thereof described herein.

In a sixth aspect, there is provided a medical device, article orimplant which is composed wholly or partly of the polyurethane orpolyurethaneurea elastomeric composition according to the above secondor third aspect, or any embodiments thereof described herein.

In a seventh aspect, there is provided process for preparing the blockcopolymer segment of Formula 1 according to the first aspect above, orany embodiments thereof described herein, whereby the process comprisesthe step of combining:

-   -   i. at least one macrodiol; or    -   ii. at least one macrodiamine; or    -   iii. a mixture of at least one macrodiol and at least one        macrodiamine, with a divalent linking compound.

In an eighth aspect, there is provided a process for preparing athermoplastic polyurethane or polyurethaneurea elastomer comprising thesilicon based block copolymer segment of Formula 1 according to thefirst aspect above, or any embodiments thereof described herein, wherebythe process comprises the steps of:

-   -   i. providing a block copolymer segment of Formula 1 according to        the first aspect above, or any embodiments thereof described        herein, or preparing a block copolymer segment of Formula 1        using the process according to the seventh aspect, or any        embodiments thereof described herein;    -   ii. optionally reacting the composition of step i. with a        divalent compound and: at least one macrodiol; at least one        macrodiamine; or a mixture of at least one macrodiol and at        least one macrodiamine; and    -   iii. reacting the block copolymer segment of step i. or step ii.        with a chain extender or a mixture of chain extenders to form        the polyurethane or polyurethaneurea elastomer

Further areas of applicability will become apparent from the descriptionprovided herein. It should be understood that the description andspecific examples are intended for the purpose of illustration only andare not intended to limit the scope of the present disclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

The drawings described herein are for illustration purposes only and arenot intended to limit the scope of the present disclosure in any way.

FIG. 1 is a perspective view of an example embodiment of a prostheticheart valve incorporating polymers disclosed herein.

DETAILED DESCRIPTION

The present disclosure describes the following various non-limitingembodiments, which relate to investigations undertaken to identifyalternative block copolymer segments for use in polyurethane/ureacompositions and polymer products thereof. It was surprisingly foundthat the block copolymer segments disclosed herein can provide a numberof advantages including enhanced soft segment properties inpolyurethane/urea thermoplastic polymers. Enhanced soft segmentproperties include an improved miscibility with hard segments andincreased inter molecular hydrogen bonding.

According to at least some embodiments described herein, the blockcopolymers, polyurethane/urea compositions and polymer products thereofcan provide advantages including:

-   -   allowing a wide range of macrodiols, including those that are        not miscible with each other, to be linked to produce a raft of        different linked macrodiols which act as “macro-monomers”;    -   the formulation of polyurethanes with low modulus, high        elasticity and high tear strength for use in cardio vascular        medical implants;    -   by utilising certain linker molecules, the synthesis of the        linked-macrodiol can be prepared prior to the        polyurethane/polyurethaneurea synthesis, without involving any        purification steps; and    -   the ability to increase the molecular weight of a        “macro-monomer” by linking two or more macrodiols or diamine        molecules, allows for the formulation of materials with a wide        range of mechanical properties, via the variation in the        relative proportions of ‘soft’ segments (for example a segment        derived from the macrodiol or macrodiamine), and hard segments        (for example a segment derived from the diisocyanate and an        optional chain extender).

Terms

With regards to the definitions provided herein, unless statedotherwise, or implicit from context, the defined terms and phrasesinclude the provided meanings. Unless explicitly stated otherwise, orapparent from context, the terms and phrases below do not exclude themeaning that the term or phrase has acquired by a person skilled in therelevant art. The definitions are provided to aid in describingparticular embodiments, and are not intended to limit the claimedinvention, because the scope of the invention is limited only by theclaims. Furthermore, unless otherwise required by context, singularterms shall include pluralities and plural terms shall include thesingular.

Herein, the term “polyurethane” relates to a polymer chain thatcomprises urethane (carbamate, —NH—COO—) links which connect monomer or“macro-monomer” units. Polyurethanes can be produced via the reaction ofmolecules containing a minimum of two isocyanate functional groups withother molecules which contain at least two alcohol (hydroxyl) groups.

Herein, the term “polyureas” relates to a polymer chain that comprisesurea links (—NH—CO—NH—) which connect monomer or “macro-monomer” units.Polyureas can be produced via the reaction of molecules containing aminimum of two isocyanate groups with other molecules which contain atleast two amine groups.

Herein, the term “polyurethaneurea” relates to a polymer chain thatcomprises both urethane and urea linking groups.

Herein, the term “macrodiol” refers to a polymeric material comprisingtwo hydroxyl groups. For example, a block copolymer segment of Formula 1with two hydroxyl groups.

Herein, the term “macrodiamine” refers to a polymeric materialcomprising two amine groups. For example, a block copolymer segment ofFormula 1 with two amine groups.

Herein, the term “polyhydrocarbon macrodiol” refers to a polymericmaterial with a polymer backbone consisting entirely of hydrogen andcarbon, and two hydroxyl groups. Examples include, but are not limitedto: poly(isobutylene)diol, poly(butadiene)diol and hydrogenatedpoly(butadiene diol).

The term “macro-monomer” refers to a polymeric substance that possessesat least one polymerisable group, for example a hydroxyl group, which iscapable of reacting with another compound, for example a diisocyanate.

Throughout the present specification, various aspects and components ofthe invention can be presented in a range format. The range format isincluded for convenience and should not be interpreted as an inflexiblelimitation on the scope of the invention. Accordingly, the descriptionof a range should be considered to have specifically disclosed all thepossible sub-ranges as well as individual numerical values within thatrange, unless specifically indicated. For example, description of arange such as from 1 to 5 should be considered to have specificallydisclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from2 to 4, from 2 to 5, from 3 to 5 etc., as well as individual and partial(except where integers are required), numbers within the recited range,for example, 1, 2, 3, 4, 5, 5.5 and 6. This applies regardless of thebreadth of the disclosed range. Where specific values are required,these will be indicated in the specification.

Herein, the term “hydrocarbon radical” refers to an optionallysubstituted straight chain, branched or cyclic, saturated andunsaturated hydrocarbon radical. The hydrocarbon radical (for examplefor substituents R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and/orR¹²) includes optionally substituted alkyl, alkenyl, alkynyl, aryl orheterocyclyl radicals.

The term “alkyl” denotes straight chain, branched or mono- orpoly-cyclic alkyl, for example C₁₋₁₈alkyls or C₃₋₈cycloalkyls. “C₁₋₁₈alkyls” and “C₃₋₈ cycloalkyls” refer to alkyl groups having 1 to 18carbon atoms or cycloalkyl groups having 3 to 8 carbon atoms.

As understood by a person skilled in the art, the term “C₁₋₁₈ alkyls”means alkyl groups with 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14,15, 16, 17 or 18 carbon atoms or a range comprising any of two of thoseintegers and including 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-8, 1-9, 1-10,1-11, 1-12, 1-13, 1-14, 1-15, 1-16, 1-17, 1-18, 2-3, 2-4, 2-5, 2-6, 2-7,2-8, 2-9, 2-10, 2-11, 2-12, 2-13, 2-14, 2-15, 2-16, 2-17, 2-18, 3-4,3-5, 3-6, 3-7, 3-8, 3-9, 3-10, 3-11, 3-12, 3-13, 3-14, 3-15, 3-16, 3-17,3-18, 4-5, 4-6, 4-7, 4-8, 4-9, 4-10, 4-11, 4-12, 4-13, 4-14, 4-15, 4-16,4-17, 4-18, 5-6, 5-7, 5-8, 5-9, 5-10, 5-11, 5-12, 5-13, 5-14, 5-15,5-16, 5-17, 5-18, 6-7, 6-8, 6-9, 6-10, 6-11, 6-12, 6-13, 6-14, 6-15,6-16, 6-17, 6-18, 7-8, 7-9, 7-10, 7-11, 7-12, 7-13, 7-14, 7-15, 7-16,7-17, 7-18, 8-9, 8-10, 8-11, 8-12, 8-13, 8-14, 8-15, 8-16, 8-17, 8-18,9-10, 9-11, 9-12, 9-13, 9-14, 9-15, 9-16, 9-17, 9-18, 10-11, 10-12,10-13, 10-14, 10-15, 10-16, 10-17, 10-18, 11-12, 11-13, 11-14, 11-15,11-16, 11-17, 11-18, 12-13, 12-14, 12-15, 12-16, 12-17, 12-18, 13-14,13-15, 13-16, 13-17, 13-18, 14-15, 14-16, 14-17, 14-18, 15-16, 15-17,15-18, 16-17, 16-18, or 17-18 carbon atoms. Examples of straight chainand branched alkyl groups include optionally substituted: methyl, ethyl,propyl, isopropyl, butyl, isobutyl, sec-butyl, amyl, isoamyl, sec-amyl,1,2-dimethylpropyl, 1,1-dimethylpropyl, pentyl, hexyl, 4-methylpentyl,1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl,2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2-dimethylbutyl,1,3-dinethylbutyl, 1,2,2-trimethylpropyl, or 1,1,2-trimethylpropyl,heptyl, 5-methylhexyl, 1-methylhexyl, 2,2-dimethylpentyl,3,3-dimethylpentyl, 4,4-dimethylpentyl, 1,2-dimethylpentyl,1,3-dimethylpentyl, 1,4-dimethylpentyl, 1,2,3-trimethylbutyl,1,1,2-trimethylbutyl, 1,1,3-trimethylbutyl, octyl, 6-methylheptyl,1-methyheptyl and 1,1,3,3-tetramethylbutyl groups, nonyl, 1-, 2-, 3-,4-, 5-, 6- or 7-methyloctyl, 1-, 2-, 3-, 4- or 5-ethylheptyl, 1-, 2- or3-propylhexyl, decyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- and 8-methylnonyl, 1-,2-, 3-, 4-, 5- or 6-ethyloctyl, 1-, 2-, 3-, or 4-propylheptyl, undecyl,1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-methyldecyl, 1-, 2-, 3-, 4-, 5-, 6-or 7-ethylnonyl. 1-, 2-, 3-, 4- or 5-propyloctyl, 1-, 2- or3-butylheptyl, 1-pentylhexyl, dodecyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-,9- or 10-methylundecyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-ethyldecyl, 1-,2-, 3-, 4-, 5- or 6-propylnonyl, 1-, 2-, 3- or 4-butyloctyl,1,2-pentylheptyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl and the like.

As understood by a person skilled in the art, the term “C₃₋₈cycloalkyls” means cycloalkyl groups with 3, 4, 5, 6, 7 or 8 carbonatoms or a range comprising any of two of those integers and including3-4, 3-5, 3-6, 3-7, 3-8, 4-5, 4-6, 4-7, 4-8, 5-6, 5-7, 5-8, 6-7, 6-8 or7-8 carbon atoms. Examples of cyclic alkyl groups include optionallysubstituted: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl and cyclooctyl groups.

The term “alkenyl” relates to groups formed from straight chain,branched or mono- or poly-cyclic alkenes including ethylenically mono-or poly-unsaturated alkyl or cycloalkyl groups as defined above, forexample C₂₋₁₈ alkenyls or C₃₋₈ cycloalkenyls. “C₂₋₁₈ alkenyls” or “C₃₋₈cycloalkenyls” refer to alkenyl or cycloalkenyl groups having 2 to 18carbon atoms or 3 to 8 carbon atoms, respectively.

As understood by a person skilled in the art, the term “C₂₋₈ alkenyls”means alkenyl groups with 2, 3, 4, 5, 6, 7 or 8 carbon atoms or a rangecomprising any of two of those integers and including 2-3, 2-4, 2-5,2-6, 2-7, 2-8, 2-9, 2-10, 2-11, 2-12, 2-13, 2-14, 2-15, 2-16, 2-17,2-18, 3-4, 3-5, 3-6, 3-7, 3-8, 3-9, 3-10, 3-11, 3-12, 3-13, 3-14, 3-15,3-16, 3-17, 3-18, 4-5, 4-6, 4-7, 4-8, 4-9, 4-10, 4-11, 4-12, 4-13, 4-14,4-15, 4-16, 4-17, 4-18, 5-6, 5-7, 5-8, 5-9, 5-10, 5-11, 5-12, 5-13,5-14, 5-15, 5-16, 5-17, 5-18, 6-7, 6-8, 6-9, 6-10, 6-11, 6-12, 6-13,6-14, 6-15, 6-16, 6-17, 6-18, 7-8, 7-9, 7-10, 7-11, 7-12, 7-13, 7-14,7-15, 7-16, 7-17, 7-18, 8-9, 8-10, 8-11, 8-12, 8-13, 8-14, 8-15, 8-16,8-17, 8-18, 9-10, 9-11, 9-12, 9-13, 9-14, 9-15, 9-16, 9-17, 9-18, 10-11,10-12, 10-13, 10-14, 10-15, 10-16, 10-17, 10-18, 11-12, 11-13, 11-14,11-15, 11-16, 11-17, 11-18, 12-13, 12-14, 12-15, 12-16, 12-17, 12-18,13-14, 13-15, 13-16, 13-17, 13-18, 14-15, 14-16, 14-17, 14-18, 15-16,15-17, 15-18, 16-17, 16-18, or 17-18 carbon atoms. As understood by aperson skilled in the art, the term “C₃₋₈ cycloalkenyls” meanscycloalkenyl groups with 3, 4, 5, 6, 7 or 8 carbon atoms or a rangecomprising any of two of those integers and including 3-4, 3-5, 3-6,3-7, 3-8, 4-5, 4-6, 4-7, 4-8, 5-6, 5-7, 5-8, 6-7, 6-8 or 7-8 carbonatoms. Examples of alkenyls and cycloalkenyls include optionallysubstituted: vinyl, allyl, 1-methylvinyl, butenyl, iso-butenyl,3-methyl-2-butenyl, 1-pentenyl, cyclopentenyl, 1-methyl-cyclopentenyl,1-hexenyl, 3-hexenyl, cyclohexenyl, 1-heptenyl, 3-heptenyl, 1-octenyl,cyclooctenyl, 1,3-butadienyl, 1,4-pentadienyl, 1,3-cyclopentadienyl,1,3-hexadienyl, 1,4-hexadienyl, 1,3-cyclohexadienyl,1,4-cyclohexadienyl, 1,3-cycloheptadienyl, 1,3,5-cycloheptatrienyl and1,3,5,7-cyclooctatetraenyl groups.

The term “alkynyl” denotes groups formed from straight chain, branched,or mono- or poly-cyclic alkynes, for example C₂₋₁₈alkynyls orC₃₋₈cycloalkynyls. Examples of alkynyl include optionally substituted:ethynyl, 1-propynyl, 1 and 2-butynyl, 2-methyl-2-propynyl, 2-pentynyl,3-pentynyl, 4-pentynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynylgroups, 10-undecynyl, 4-ethyl-1-octyn-3-yl, 7-dodecynyl, 9-dodecynyl,10-dodecynyl, 3-methyl-2-dodecyn-3-yl, 2-tridecynyl, 11-tridecynyl,3-tetradecynyl, 7-hexadecynyl and 3-octadecynyl.

The term “aryl” denotes single, polynuclear, conjugated and fusedresidues of aromatic hydrocarbons. Examples of aryl include optionallysubstituted: phenyl, biphenyl, terphenyl, quaterphenyl, phenoxyphenyl,naphthyl, tetrahydronaphthyl, anthracenyl, dihydroanthracenyl,benzanthracenyl, dibenzanthracenyl and phenanthrenyl groups.

The term “heterocyclyl” denotes mono- or poly-cyclic heterocyclyl groupscontaining at least one heteroatom selected from nitrogen, sulphur andoxygen. Suitable heterocyclyl groups include optionally substituted:N-containing heterocyclic groups, such as, unsaturated 3 to 6 memberedheteromonocyclic groups containing 1 to 4 nitrogen atoms, for example,pyrrolyl, pyrrolinyl, imidazolyl, pyrazolyl, pyridyl, pyrimidinyl,pyrazinyl, pyridazinyl, triazolyl or tetrazolyl; saturated 3 to6-membered heteromonocyclic groups containing 1 to 4 nitrogen atoms,such as pyrrolidinyl, imidazolidinyl, piperidino or piperazinyl;unsaturated condensed heterocyclic groups containing 1 to 5 nitrogenatoms, such as, indolyl, isoindolyl, indolizinyl, benzimidazolyl,quinolyl, isoquinolyl, indazolyl, benzotriazolyl ortetrazolopyridazinyl; unsaturated 3 to 6-membered heteromonocyclic groupcontaining an oxygen atom, such as, pyranyl or furyl; unsaturated 3 to6-membered hetermonocyclic group containing 1 to 2 sulphur atoms, suchas, thienyl; unsaturated 3 to 6-membered heteromonocyclic groupcontaining 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms, such as,oxazolyl, isoazolyl or oxadiazolyl; saturated 3 to 6-memberedheteromonocyclic group containing 1 to 2 oxygen atoms and 1 to 3nitrogen atoms, such as, morpholinyl; unsaturated condensed heterocyclicgroup containing 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms, such as,benzoxazolyl or benzoxadiazolyl; unsaturated 3 to 6-memberedheteromonocyclic group containing 1 to 2 sulphur atoms and 1 to 3nitrogen atoms, such as thiazolyl or thiadiazolyl; saturated 3 to6-membered heteromonocyclic group containing 1 to 2 sulphur atoms and 1to 3 nitrogen atoms, such as, thiadiazolyl; and unsaturated condensedheterocyclic group containing 1 to 2 sulphur atoms and 1 to 3 nitrogenatoms, such as benzothiazolyl or benzothiadiazolyl groups.

Herein, “optionally substituted” means that a group may or may not befurther substituted with one or more groups selected from oxygen,nitrogen, sulphur, alkyl, alkenyl, alkynyl, aryl, halo, haloalkyl,haloalkenyl, haloalkynyl, haloaryl, hydroxy, alkoxy, alkenyloxy,alkynyloxy, aryloxy, carboxy, benzyloxy, haloalkoxy, haloalkenyloxy,haloalkynyloxy, haloaryloxy, nitro, nitroalkyl, nitroalkenyl,nitroalkynyl, nitroaryl, nitroheterocyclyl, azido, amino, alkylamino,alkenylamino, alkynylamino, arylamino, benzylamino, acyl, alkenylacyl,alkynylacyl, arylacyl, acylamino, acyloxy, aldehydo, alkylsulphonyl,arylsulphonyl, alkyl sulphonylamino, aryl sulphonylamino,alkylsulphonyloxy, arylsulphonyloxy, heterocyclyl, heterocycloxy,heterocyclylamino, haloheterocyclyl, alkylsulphenyl, arylsulphenyl,carboalkoxy, carboaryloxy, mercapto, alkylthio, arylthio, acylthio andthe like. It will be appreciated that the term “optionally substituted”may also be referred to as “substituted or unsubstituted”.

Block Copolymer Segments

Disclosed herein are block copolymer segments of Formula 1 for athermoplastic polyurethane or polyurethaneurea elastomer composition:

wherein

A¹ is an endcapping group;

A² is hydrogen or an endcapping group;

each Y¹ and Y² are independently selected from a polysiloxane macrodiol,polysiloxane macrodiamine, polyether macrodiol, polycarbonate macrodiol,polyester macrodiol, and a polyhydrocarbon macrodiol;

each L¹ and L² is a divalent linking group independently selected fromurethane, urea carbonate, amide, ester, and phosphonate;

n is an integer of 1 to 5;

t is an integer of 0 to 5; and

Q is selected from a moiety of Formula A or Formula B:

wherein

R¹, R², R³, and R⁴, are each independently selected from hydrogen and anoptionally substituted straight chain, branched or cyclic, saturated andunsaturated hydrocarbon radical;

R⁵ and R⁶ are each independently selected from a straight chain,branched or cyclic, saturated and unsaturated hydrocarbon radicaloptionally interrupted with one or more heteroatoms independentlyselected from O, N and S;

m is an integer of 1 to 50;

X is a group selected from OC(O)O, C(O)O and O; and

q is an integer of 1 to 50; and r is an integer of 2 to 50.

The block copolymer segment may be a block copolymer segment of Formula1A:

wherein each A¹, A², Y¹, L¹, L², Y², R¹, R², R³, R⁴, R⁵, R⁶, m, n and t,are as defined herein.

The block copolymer segment may be a block copolymer segment of Formula1A(i):

wherein each A¹, A², L², Y², R¹, R², R³, R⁴, R⁵, R⁶, m and n, are asdefined herein.

The block copolymer segment may be a block copolymer segment of Formula1A(i)(a):

wherein each A¹, A², L², R¹, R², R³, R⁴, R⁵, R⁶, X, m, q and r, are asdefined herein.

The block copolymer segment may be a block copolymer segment of Formula1A(i)(b):

wherein each A¹, A², L², R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹,R¹², m, n and u, are as defined herein.

The block copolymer segment may be a block copolymer segment of Formula1A(ii):

wherein each A¹, A², L¹, L², R¹, R², R³, R⁴, R⁵, R⁶, X, m, q, r and t,are as defined herein.

The block copolymer segment may be a block copolymer segment of Formula1B:

wherein each A¹, A², Y¹, L¹, L², Y², X, n, r, t, and q, are as definedherein.

The block copolymer segment may be a block copolymer segment of Formula1B(i):

wherein each A¹, A², L², Y², X, q, r and n, are as defined herein.

The block copolymer segment may be a block copolymer segment of Formula1B(i)(a):

wherein

n is an integer from 1 to 5;

A¹ is an endcapping group;

A² is hydrogen or an endcapping group;

X and X¹ are each independently selected from OC(O)O, C(O)O and O;

q and v are each independently selected from an integer of 1 to 50 (forexample 5 to 20); and

r and w are each independently selected from an integer of 2 to 50.

The block copolymer segment may be a block copolymer segment of Formula1B(i)(b):

wherein each A¹, A², q, X, and r, are as defined in claim 1, and L², n,R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹² and u, are as defined herein.

The block copolymer segment may be a block copolymer segment of Formula1B(ii):

wherein each A¹, A², L¹, L², X, n, q, r and t, are as defined in claim1, and each R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹² and u, are as defined herein.

Substituent Q

Substituent Q may be selected from a moiety of Formula A or Formula B asdescribed herein.

Substituent Q may be selected from a moiety of Formula A:

-   -   wherein    -   R¹, R², R³, and R⁴, are each independently selected from        hydrogen and an optionally substituted straight chain, branched        or cyclic, saturated and unsaturated hydrocarbon radical;    -   R⁵ and R⁶ are each independently selected from a straight chain,        branched or cyclic, saturated and unsaturated hydrocarbon        radical optionally interrupted with one or more heteroatoms        independently selected from O, N and S; and    -   m is an integer of 1 to 50.

Substituent Q may be selected from a moiety of Formula B:

-   -   wherein    -   X is a group selected from OC(O)O, C(O)O and O;    -   q is an integer of 1 to 50; and    -   r is an integer of 2 to 50.

In one embodiment substituent Q is a moiety of Formula A. Q may be α,ωbis-(6-hydroxyethoxypropyl)polydimethylsiloxane. In another embodimentsubstituent Q is a moiety of Formula B.

Substituent A¹

Herein, substituent A¹ is an “endcapping group” and includes reactivefunctional groups or groups containing reactive functional groups.Examples of suitable reactive functional groups for substituent A¹include: hydroxyl groups, carboxylic acids, aldehydes, ketones, esters,acid halides, acid anhydrides, amine groups, imine groups, thio groups,thioesters, sulphonic acids and epoxides.

A¹ may be selected from hydroxyl or amine. In one embodiment, A¹ is ahydroxyl group. In another embodiment, A¹ is an amine group.

Substituent A²

Herein substituent A² is hydrogen or an “endcapping group” and includesreactive functional groups or groups containing reactive functionalgroups. Examples of suitable reactive functional groups for substituentA² include: hydroxyl groups, carboxylic acids, aldehydes, ketones,esters, acid halides, acid anhydrides, amine groups, imine groups, thiogroups, thioesters, sulphonic acids and epoxides.

A² may be selected from hydrogen, hydroxyl or amine. In one embodimentA² is hydrogen. In another embodiment A² is a hydroxyl group. In anotherembodiment A² is an amine group.

Substituents Y¹ and Y²

Herein each individual substituent Y¹ and Y² are independently selectedfrom a polysiloxane macrodiol, polysiloxane macrodiamine, polyethermacrodiol, polycarbonate macrodiol, polyester macrodiol, and apolyhydrocarbon macrodiol.

At least one of Y¹ and Y² may be a polysiloxane macrodiol. Y¹ may be apolysiloxane macrodiol. Y² may be a polysiloxane macrodiol.

Examples of polysiloxane macrodiols include, but are not limited to:polydimethylsiloxane diols, such as α,ωbis-(6-hydroxyethoxypropyl)polydimethylsiloxane, α,ωbis-(4-hydroxybutyl)polydimethylsiloxane and α,ωbis-(3-hydroxypropyl)polydimethylsiloxane.

In one embodiment at least one of Y¹ and Y² is a polydimethylsiloxanediol. In another embodiment both of Y¹ and Y² are polydimethylsiloxanediols. In another embodiment at least one of Y¹ and Y² is α,ωbis-(6-hydroxyethoxypropyl)polydimethylsiloxane. In another embodimentboth of Y¹ and Y² are α,ωbis-(6-hydroxyethoxypropyl)polydimethylsiloxane.

At least one of Y¹ and Y² may be a polysiloxane macrodiamine. Y¹ may bea polysiloxane macrodiamine. Y² may be a polysiloxane macrodiamine.

Examples of polysiloxane macrodiamines include, but are not limited to:α,ω bis-(aminomethyl)polydimethylsiloxane, α,ωbis-(2-aminoethyl)polydimethylsiloxane, p, wbis-(3-aminopropyl)polydimethylsiloxane, α,ωbis-(4-aminobutyl)polydimethylsiloxane, α,ωbis-(5-aminopentyl)polydimethylsiloxane and the like.

At least one of Y¹ and Y² may be a polyether macrodiol. Y¹ may be apolyether macrodiol. Y² may be a polyether macrodiol.

Examples of polyether macrodiols include, but are not limited to:poly(ethylene oxide), poly(propylene oxide), poly(butylene oxide),poly(pentylene oxide), poly(hexamethylene oxide) (PHMO),poly(heptamethylene oxide), poly(octamethylene oxide) (POMO) andpoly(decamethylene oxide) (PDMO).

In one embodiment at least one of Y¹ and Y² is poly(hexamethylene oxide)(PHMO).

In one embodiment both of Y¹ and Y² are poly(hexamethylene oxide)(PHMO).

At least one of Y¹ and Y² may be a polycarbonate macrodiol. Y¹ may be apolycarbonate macrodiol. Y² may be a polycarbonate macrodiol.

Examples of polycarbonate macrodiols include, but are not limited to:poly(propylene carbonate), poly(hexamethylene carbonate) andpolycarbonate and copolycarbonate macrodiols can be prepared by using anester interchange reaction as described in P. A. Gunatillake et al.,Journal of Applied Polymer Science, 69(8) 1621-1633, (1998), for exampleby reacting a carbonate such as ethylene carbonate with a diol.Appropriate diols include, but are not limited to: 1,6-hexanediol,1,10-decanediol, 2,2-diethyl-1,3-propanediol, 1,4-cyclohexanedimethanoland bis(4-hydroxybutyl)-1,1,3,3-tetramethyldisiloxane.

At least one of Y¹ and Y² may be a polyester macrodiol. Y¹ may be apolyester macrodiol. Y² may be a polyester macrodiol.

Examples of polyester macrodiols include, but are not limited to:poly(caprolactone) diol, poly(tetramethyleneadipate) diol,poly(D,L-lactide) and, poly(glycolide).

At least one of Y¹ and Y² may be a polyhydrocarbon macrodiol. Y¹ may bea polyhydrocarbon macrodiol. Y² may be a polyhydrocarbon macrodiol.

Examples of polyhydrocarbon macrodiols include polymeric aliphaticα,ω-diols. Specific examples of polyhydrocarbon macrodiols include, butare not limited to: poly(isobutylene)diol and poly(butadiene)diols, suchas hydrogenated poly(butadiene)diols (including fully hydrogenatedpoly(butadiene)diols).

In one embodiment, Y¹ and Y² are each independently selected from amoiety of Formula A′ or Formula B′:

wherein

R⁷, R⁸, R⁹, and R¹⁰, are each independently selected from hydrogen andan optionally substituted straight chain, branched or cyclic, saturatedand unsaturated hydrocarbon radical; and

R¹ and R¹² are each independently selected from a straight chain,branched or cyclic, saturated and unsaturated hydrocarbon radicaloptionally interrupted with one or more heteroatoms independentlyselected from O, N and S; and

u is an integer of 1 to 50; or

wherein

X¹ is a group selected from OC(O)O, C(O)O and O;

v is an integer of 1 to 50, for example an integer of 5 to 20; and

w is an integer of 2 to 50.

In one embodiment at least one of Y¹ and Y² is a moiety of Formula A′.

In one embodiment at least one of Y¹ and Y² is a moiety of Formula B′.

In another embodiment substituents Y¹ and Y² are the same.

In yet another embodiment substituents Y¹ and Y² are different. It willbe appreciated that Y¹ and Y² may be selected from different groupswithin same individual Formula A′. Similarly, it will also beappreciated that Y¹ and Y² may be selected from different groups withinsame individual Formula B′.

Substituents L¹ and L²

Herein substituents L¹ and L² are divalent linking groups independentlyselected from urethane, urea carbonate, amide, ester, and phosphonatelinking groups.

At least one of L¹ or L² may be a urethane linking group. L¹ may be aurethane linking group. L² may be a urethane linking group.

Urethane linking groups can be produced by reacting hydroxyl containingcompounds, such as a macrodiol, with a diisocyanate. Examples ofappropriate diisocyanates include aliphatic, cyclic or aromaticdiisocyanates such as, for example: 1,4-diisocyanatobutane,1,12-diisocyanatododecane, 1,6-diisocyantehexane,1,8-diisocyanateoctane, 4,4′-methylenediphenyl diisocyanate (MDI),4,4′-methylenebis(cyclohexyl diisocyanate) (H12MDI), p-phenylenediisocyanate (p-PDI), m-phenylene diisocyanate (m-PDI)trans-cyclohexane-1,4-diisocyanate (CHDI) or a mixture of the cis andtrans isomers, 1,6-hexamethylene diisocyanate (HDI), 2,4-toluenediisocyanate (2,4-TDI) or its isomers (for example 2,6-toluenediisocyanate (2,6-TDI)), or mixtures thereof, p-tetramethylxylenediisocyanate (p-TMXDI), isophorone diisocyanate or m-tetramethylxylenediisocyanate (m-TMXDI), 1,6-diisocyanatohexane (DICH),1,3-bis(1-isocyanato-1-methylethyl)benzene, or1,5-diisocyanatonaphthalene (NDI).

In one embodiment, L¹ or L² may be independently a linking group ofFormula E:

wherein R^(a) is selected from:

-   -   an optionally substituted straight chain, branched or cyclic,        saturated or unsaturated hydrocarbon radical (including        optionally substituted alkyl, alkenyl, alkynyl, aryl or        heterocyclyl radicals).

For example, L¹ or L² may be selected from:

At least one of L¹ or L² may be a urea linking group. L¹ may be a urealinking group. L² may be a urea linking group.

Urea linking groups can be produced by reacting amine containingcompounds, such as a macrodiamine, with a diisocyanate. Examples ofappropriate diisocyanates include aliphatic, cyclic or aromaticdiisocyanates such as, for example: 1,4-diisocyanatobutane,1,12-diisocyanatododecane, 1,6-diisocyantehexane,1,8-diisocyanateoctane, 4,4′-methylenediphenyl diisocyanate (MDI),4,4′-methylenebis(cyclohexyl diisocyanate) (H12MDI), p-phenylenediisocyanate (p-PDI), m-phenylene diisocyanate (m-PDI)trans-cyclohexane-1,4-diisocyanate (CHDI) or a mixture of the cis andtrans isomers, 1,6-hexamethylene diisocyanate (HDI), 2,4-toluenediisocyanate (2,4-TDI) or its isomers (for example 2,6-toluenediisocyanate (2,6-TDI)), or mixtures thereof, p-tetramethylxylenediisocyanate (p-TMXDI), isophorone diisocyanate or m-tetramethylxylenediisocyanate (m-TMXDI), or 1,5-diisocyanatonaphthalene (NDI).

In one embodiment, L¹ or L² may be independently a linking group ofFormula F:

wherein R^(b) is selected from:

-   -   an optionally substituted straight chain, branched or cyclic,        saturated or unsaturated hydrocarbon radical (including        optionally substituted alkyl, alkenyl, alkynyl, aryl or        heterocyclyl radicals).

For example, L¹ or L² may be selected from:

At least one of L¹ or L² may be a carbonate linking group. L¹ may be acarbonate linking group. L² may be a carbonate linking group.

In one embodiment, L¹ or L² may be independently a linking group ofFormula G:

wherein R^(c) is selected from:

-   -   an optionally substituted straight chain, branched or cyclic,        saturated or unsaturated hydrocarbon radical (including        optionally substituted alkyl, alkenyl, alkynyl, aryl or        heterocyclyl radicals).

At least one of L¹ or L² may be an amide linking group. L¹ may be anamide linking group. L² may be an amide linking group.

Examples of amide linking groups include —C(O)NH— groups.

At least one of L¹ or L² may be an ester linking group. L¹ may be anester linking group. L² may be an ester linking group.

Examples of ester linking groups include, but are not limited to, estersformed through the reactions between alcohols and aliphatic or aromaticdi-acid or diacid chloride containing compounds.

At least one of L¹ or L² may be a phosphonate linking group. L¹ may be aphosphonate linking group. L² may be a phosphonate linking group.

L¹ or L² may be independently a linking group of Formula H:

wherein:

-   -   each of R^(d), and R^(f) is each independently selected from: an        optionally substituted straight chain, branched or cyclic,        saturated or unsaturated hydrocarbon radical (including        optionally substituted alkyl, alkenyl, alkynyl, aryl or        heterocyclyl radicals); and    -   R^(e) is selected from: hydrogen; or an optionally substituted        straight chain, branched or cyclic, saturated or unsaturated        hydrocarbon radical (including optionally substituted alkyl,        alkenyl, alkynyl, aryl or heterocyclyl radicals). For example,        substituent R^(e) may be an optionally substituted methyl group.

In one embodiment substituents L¹ and L² are the same. In anotherembodiment substituents L¹ and L² are different.

Substituents R¹, R², R³, R⁴, R⁵. R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹²

Herein, R¹, R², R³, R⁴, R⁷, R⁸, R⁹, and R¹⁰ are each independentlyselected from hydrogen and an optionally substituted straight chain,branched or cyclic, saturated and unsaturated hydrocarbon radical.

Herein, R⁵, R⁶, R¹¹ and R¹² are each independently selected from anoptionally substituted straight chain, branched or cyclic, saturated andunsaturated hydrocarbon radical optionally interrupted with one or moreheteroatoms independently selected from O, N and S.

In one embodiment at least one of R¹, R², R³, and R⁴ is an optionallysubstituted alkyl group. For example at least one of R¹, R², R³, and R⁴is a methyl group.

In one embodiment each of R¹, R², R³, and R⁴ is an optionallysubstituted alkyl group. For example each of R¹, R², R³, and R⁴ is amethyl group.

In one embodiment at least two of R¹, R², R³, and R⁴ are the samesubstituent.

In one embodiment all of R¹, R², R³, and R⁴ are the same substituent.

In another embodiment at least one of R⁵ and R⁶ is independentlyselected from optionally substituted: propylene, butylene, pentylene,hexylene, ethoxypropyl, propoxypropyl and butoxypropyl groups.

In another embodiment both of R⁵ and R⁶ are selected from optionallysubstituted: propylene, butylene, pentylene, hexylene, ethoxypropyl,propoxypropyl and butoxypropyl groups.

In another embodiment at least one of R⁵ and R⁶ is independentlyselected from the moiety of Formula D:

wherein c is an integer between 1 and 6; and d is an integer between 1and 6. For example c is 2 and/or d is 3.

In one embodiment R⁵ and R⁶ are the same substituent.

In one embodiment R⁵ and R⁶ are different substituents.

In one embodiment at least one of R⁷, R⁸, R⁹, and R¹⁰ is an optionallysubstituted alkyl group. For example at least one of R⁷, R⁸, R⁹, and R¹⁰is a methyl group.

In one embodiment each of R⁷, R⁸, R⁹, and R¹⁰ is an optionallysubstituted alkyl group.

For example each of R⁷, R⁸, R⁹, and R¹⁰ is a methyl group.

In one embodiment at least two of R⁷, R⁸, R⁹, and R¹⁰ are the samesubstituent.

In one embodiment all of R⁷, R⁸, R⁹, and R¹⁰ are the same substituent.

In another embodiment at least one of R¹¹ and R¹² is independentlyselected from optionally substituted: propylene, butylene, pentylene,hexylene, ethoxypropyl, propoxypropyl and butoxypropyl groups.

In another embodiment both of R¹¹ and R¹² are selected from optionallysubstituted: propylene, butylene, pentylene, hexylene, ethoxypropyl,propoxypropyl and butoxypropyl groups.

In one embodiment, at least one of R¹¹ and R¹² is independently selectedfrom the moiety

wherein a is an integer between 1 and 6; and b is an integer between 1and 6. For example a is 2 and/or b is 3.

In one embodiment R¹¹ and R¹² are the same substituent. In anotherembodiment R¹¹ and R¹² are different substituents.

Substituents X and X¹

Herein, substituent X and X¹ may be independently selected from OC(O)O,C(O)O and O.

X may be OC(O)O. X may be C(O)O. X may be O. X¹ may be OC(O)O. X¹ may beC(O)O. X¹ may be O. X and X¹ may be the same. X and X¹ may be different.

Integers a, b, m, m′, m″, n, q, q, q″, r, r′, r″, t, u and v

Integer a may be: 1 or 2 or 3 or 4 or 5 or 6. In one embodiment, integera is 2. In another embodiment, integer a is 3.

Integer b may be: 1 or 2 or 3 or 4 or 5 or 6. In one embodiment, integerb is 2. In another embodiment integer b is 3.

Herein integer m may be: 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10or 11 or 12 or 13 or 14 or 15 or 16 or 17 or 18 or 19 or 20 or 21 or 22or 23 or 24 or 25 or 26 or 27 or 28 or 29 or 30 or 31 or 32 or 33 or 34or 35 or 36 or 37 or 38 or 39 or 40 or 41 or 42 or 43 or 44 or 45 or 46or 47 or 48 or 49 or 50.

Herein integer m′ may be: 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or10 or 11 or 12 or 13 or 14 or 15 or 16 or 17 or 18 or 19 or 20 or 21 or22 or 23 or 24 or 25 or 26 or 27 or 28 or 29 or 30 or 31 or 32 or 33 or34 or 35 or 36 or 37 or 38 or 39 or 40 or 41 or 42 or 43 or 44 or 45 or46 or 47 or 48 or 49 or 50.

Herein integer m″ may be: 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or10 or 11 or 12 or 13 or 14 or 15 or 16 or 17 or 18 or 19 or 20 or 21 or22 or 23 or 24 or 25 or 26 or 27 or 28 or 29 or 30 or 31 or 32 or 33 or34 or 35 or 36 or 37 or 38 or 39 or 40 or 41 or 42 or 43 or 44 or 45 or46 or 47 or 48 or 49 or 50.

Herein integer n may be: 1 or 2 or 3 or 4 or 5.

Herein integer t may be: 0 or 1 or 2 or 3 or 4 or 5.

In one embodiment integer t is 0.

Herein integer q may be: 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10or 11 or 12 or 13 or 14 or 15 or 16 or 17 or 18 or 19 or 20 or 21 or 22or 23 or 24 or 25 or 26 or 27 or 28 or 29 or 30 or 31 or 32 or 33 or 34or 35 or 36 or 37 or 38 or 39 or 40 or 41 or 42 or 43 or 44 or 45 or 46or 47 or 48 or 49 or 50.

In one embodiment integer q is 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12or 13 or 14 or 15 or 16 or 17 or 18 or 19 or 20.

Herein integer q′ may be: 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or10 or 11 or 12 or 13 or 14 or 15 or 16 or 17 or 18 or 19 or 20 or 21 or22 or 23 or 24 or 25 or 26 or 27 or 28 or 29 or 30 or 31 or 32 or 33 or34 or 35 or 36 or 37 or 38 or 39 or 40 or 41 or 42 or 43 or 44 or 45 or46 or 47 or 48 or 49 or 50.

In one embodiment integer q′ is 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12or 13 or 14 or 15 or 16 or 17 or 18 or 19 or 20.

Herein integer q″ may be: 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or10 or 11 or 12 or 13 or 14 or 15 or 16 or 17 or 18 or 19 or 20 or 21 or22 or 23 or 24 or 25 or 26 or 27 or 28 or 29 or 30 or 31 or 32 or 33 or34 or 35 or 36 or 37 or 38 or 39 or 40 or 41 or 42 or 43 or 44 or 45 or46 or 47 or 48 or 49 or 50.

In one embodiment integer q″ is 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12or 13 or 14 or 15 or 16 or 17 or 18 or 19 or 20.

Herein integer r may be: 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or11 or 12 or 13 or 14 or 15 or 16 or 17 or 18 or 19 or 20 or 21 or 22 or23 or 24 or 25 or 26 or 27 or 28 or 29 or 30 or 31 or 32 or 33 or 34 or35 or 36 or 37 or 38 or 39 or 40 or 41 or 42 or 43 or 44 or 45 or 46 or47 or 48 or 49 or 50.

Herein integer r′ may be: 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or11 or 12 or 13 or 14 or 15 or 16 or 17 or 18 or 19 or 20 or 21 or 22 or23 or 24 or 25 or 26 or 27 or 28 or 29 or 30 or 31 or 32 or 33 or 34 or35 or 36 or 37 or 38 or 39 or 40 or 41 or 42 or 43 or 44 or 45 or 46 or47 or 48 or 49 or 50.

Herein integer r″ may be: 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or11 or 12 or 13 or 14 or 15 or 16 or 17 or 18 or 19 or 20 or 21 or 22 or23 or 24 or 25 or 26 or 27 or 28 or 29 or 30 or 31 or 32 or 33 or 34 or35 or 36 or 37 or 38 or 39 or 40 or 41 or 42 or 43 or 44 or 45 or 46 or47 or 48 or 49 or 50.

Herein integer u may be: 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10or 11 or 12 or 13 or 14 or 15 or 16 or 17 or 18 or 19 or 20 or 21 or 22or 23 or 24 or 25 or 26 or 27 or 28 or 29 or 30 or 31 or 32 or 33 or 34or 35 or 36 or 37 or 38 or 39 or 40 or 41 or 42 or 43 or 44 or 45 or 46or 47 or 48 or 49 or 50.

Herein integer v may be: 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10or 11 or 12 or 13 or 14 or 15 or 16 or 17 or 18 or 19 or 20 or 21 or 22or 23 or 24 or 25 or 26 or 27 or 28 or 29 or 30 or 31 or 32 or 33 or 34or 35 or 36 or 37 or 38 or 39 or 40 or 41 or 42 or 43 or 44 or 45 or 46or 47 or 48 or 49 or 50.

In one embodiment integer v is 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12or 13 or 14 or 15 or 16 or 17 or 18 or 19 or 20.

Herein integer w may be: 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or11 or 12 or 13 or 14 or 15 or 16 or 17 or 18 or 19 or 20 or 21 or 22 or23 or 24 or 25 or 26 or 27 or 28 or 29 or 30 or 31 or 32 or 33 or 34 or35 or 36 or 37 or 38 or 39 or 40 or 41 or 42 or 43 or 44 or 45 or 46 or47 or 48 or 49 or 50.

It will be appreciated that the above integer embodiments includes anyinteger range thereof. For example, a range may be provided between anytwo integers selected from each of the above described integerembodiments of a, b, m, n, q, r, t, u, v and w.

The block copolymer segment of Formula 1 according to any of the abovedescribed embodiments may have a molecular weight range between about400 and 6000, or about 400 and 4000, or about 800 and 1600. Unlessstated otherwise, herein the phrase “molecular weight” refers to thenumber-average molecular weight (M_(n)) of a particular polymer.

Thermoplastic Polyurethane or Polyurethaneurea Elastomer Compositions

Disclosed herein is a thermoplastic polyurethane or polyurethaneureaelastomer composition comprising a plurality of soft segments and hardsegments, wherein the plurality of soft segments are each derived fromat least one block copolymer segment of Formula 1 as defined herein andoptionally an additional polyol or polyamine.

A thermoplastic polyurethane or polyurethaneurea elastomer compositionmay be provided comprising a plurality of soft segments and hardsegments, wherein the plurality of soft segments are each derived from asingle type of block copolymer segment selected from a block copolymersegment of Formula 1 as defined herein and optionally an additionalpolyol or polyamine.

Also disclosed herein is a thermoplastic polyurethane orpolyurethaneurea elastomer composition comprising a plurality of softsegments and hard segments, wherein the plurality of soft segments areeach derived from a mixture of two separate block copolymer segments ofFormula 1 as defined herein and optionally an additional polyol orpolyamine.

Also disclosed herein are thermoplastic polyurethane or polyurethaneureaelastomer compositions comprising a reaction product of:

-   -   i. at least one block copolymer segment of Formula 1 as defined        herein;    -   ii. a diisocyanate;    -   iii. one or more chain extenders; and    -   iv. optionally an additional polyol or polyamine.

Herein, the thermoplastic polyurethane or polyurethaneurea elastomercomposition may have a tensile strength of ≥5 MPa. For example thethermoplastic polyurethane or polyurethaneurea elastomer composition mayhave a tensile strength of: ≥7.5 MPa, or ≥10 MPa, or ≥12.5 MPa, or ≥15MPa, or ≥17.5 MPa, or ≥20 MPa, or ≥22.5 MPa, or ≥25 MPa, or ≥27.5 MPa,or ≥30 MPa, or ≥32.5 MPa, or ≥35 MPa, or ≥37.5 MPa, or ≥40 MPa, or ≥42.5MPa, or ≥45 MPa, or ≥47.5 MPa, or ≥50 MPa.

Herein, the thermoplastic polyurethane or polyurethaneurea elastomercomposition may have a Young's Modulus of ≥10 MPa. For example thethermoplastic polyurethane or polyurethaneurea elastomer composition mayhave a Young's Modulus of: ≥12.5 MPa, or ≥15 MPa, or ≥17.5 MPa, or ≥20MPa, or ≥22.5 MPa, or ≥25 MPa, or ≥27.5 MPa, or ≥30 MPa, or ≥32.5 MPa,or ≥35 MPa, or ≥37.5 MPa, or ≥40 MPa, or ≥42.5 MPa, or ≥45 MPa, or ≥47.5MPa, or ≥50 MPa, or ≥52.5 MPa, or ≥55 MPa, or ≥57.5 MPa, or ≥60 MPa, or≥62.5 MPa, or ≥65 MPa, or ≥67.5 MPa, or ≥70 MPa, or ≥72.5 MPa, or ≥75MPa, or ≥77.5 MPa, or ≥80 MPa.

Herein, the thermoplastic polyurethane or polyurethaneurea elastomercomposition may have an elongation at break of ≥500%. For example thethermoplastic polyurethane or polyurethaneurea elastomer composition mayhave an elongation at break of: ≥550%, or ≥600%, or ≥650%, or ≥700%, or≥750%, or ≥800%, or ≥850%, or ≥900%, or ≥950%, or ≥1000%, or ≥1050%, or≥1100%, or ≥1150%, or ≥1200%, or ≥1250%, or ≥1300%, or ≥1350%, or≥1400%, or ≥1450%, or ≥1500%, or ≥1550%, or ≥1600%, or ≥1650%, or≥1700%, or ≥1750%, or ≥1800%, or ≥1850%, or ≥1900%, or ≥1950%, or≥2000%.

It will be appreciated that these tensile strengths may be measuredusing standard industry methods, for example a method adopted from ASTMStandard Method for thin Plastic Sheeting (e.g. ASTM D 882-02). In afurther example, the method may involve thin films, for example about200 to 300 microns, using the ASTM D 882-02 test method.

Example conditions which may be used to measure the tensile strength ofa sample with ASTM D 882-02 method are:

-   -   using dumbbell shaped specimens which are 75 mm in length, 13 mm        in width at each end and 4 mm at the central narrow section        (with a constant width over at least 15 mm of length); and    -   using an Instron 5565 fitted with static load cell ±100 N and        calibrated using Instron Bluehill 2 (version 2.35) software.

For the tensile test with dry conditions, the specimen may be:

-   -   fixed between upper and lower grips (for example Instron grips)        such that the gap between the grips is 10 mm;    -   stretching the 10 mm long section of film at a rate of 50 mm per        minute until the film breaks;    -   performing at least three replicates, for example three, four or        five replicates.

For the tensile test with wet conditions, or replicating the conditionsfound for medical applications, the specimen may be:

-   -   placed in a plastic bag and immersed in water maintained at        37° C. for at least two hours;    -   dried using tissue paper and fixed between upper and lower grips        (for example Instron grips) such that the gap between the grips        is 10 mm;    -   stretched at a rate of 100 mm per min until the film breaks.

Stress, strain, breaking stress and elongation at breaking can beobtained using either the dry or wet conditions from the InstronBluehill 2 (version 2.35) software. These parameters allow one to obtainvalues for the tensile strength, the Young's modulus (stiffness) andElongation (elasticity) for a sample.

Herein, the thermoplastic polyurethane or polyurethaneurea elastomercomposition may have a polydispersity index (PDI) of ≤3.00. For examplethe thermoplastic polyurethane or polyurethaneurea elastomer compositionmay have a polydispersity index (PDI) of: ≤2.90, or ≤2.80, or ≤2.70, or≤2.60, or ≤2.50, or ≤2.40, or ≤2.30, or ≤2.20, or ≤2.10, or ≤2.00, or≤1.90, or ≤1.80, or ≤1.70, or ≤1.60, or ≤1.50, or ≤1.40, or ≤1.30, or≤1.20, or ≤1.10.

In one embodiment a single block copolymer segment of Formula 1 is usedin the formulation of the thermoplastic polyurethane or polyurethaneureaelastomer composition.

In another embodiment two different block copolymer segments of Formula1 are used in the formulation of the thermoplastic polyurethane orpolyurethaneurea elastomer composition.

Examples of mixtures one or two different block copolymer segments ofFormula 1 or a combination of a block copolymer of Formula 1 and amacrodiol, which are used in the formulation of a thermoplasticpolyurethane or polyurethaneurea elastomer composition, are shown inTable 1. Here Segment 1 and/or Segment 2 can be added in a reactionmixture with one or more chain extenders, a diisocyanate, to produce athermoplastic polyurethane or polyurethaneurea elastomer composition. Inthese examples R^(5a) and R^(6a) may both be (CH₂)₂O(CH₂)₄.

TABLE 1 Examples of one or two different block copolymer segments ofFormula 1, or a combination of a block copolymer of Formula 1 and amacrodiol, which are used in the formulation of a thermoplasticpolyurethane or polyurethaneurea elastomer composition. In the followingexamples, R^(5a), R^(6a), m′ and r are as defined herein. Segment Numberfor Block Specific Segment Group Copolymer for Block Copolymer 1 Segment1

Segment 2 — 2 Segment 1

Segment 2 — 3 Segment 1

Segment 2 — 4 Segment 1

Segment 2 — 5 Segment 1

Segment 2

6 Segment 1

Segment 2

7 Segment 1

Segment 2

8 Segment 1

Segment 2

Diisocyanates

Examples of appropriate diisocyanates include aliphatic, cyclic oraromatic diisocyanates such as, for example: 1,4-diisocyanatobutane,1,12-diisocyanatododecane, 1,6-diisocyantehexane,1,8-diisocyanateoctane, 4,4′-methylenediphenyl diisocyanate (MDI),4,4′-methylenebis(cyclohexyl diisocyanate) (H12MDI), p-phenylenediisocyanate (p-PDI), m-phenylene diisocyanate (m-PDI)trans-cyclohexane-1,4-diisocyanate (CHDI) or a mixture of the cis andtrans isomers, 1,6-hexamethylene diisocyanate (HDI), 2,4-toluenediisocyanate (2,4-TDI) or its isomers (for example 2,6-toluenediisocyanate (2,6-TDI)), or mixtures thereof, p-tetramethylxylenediisocyanate (p-TMXDI), isophorone diisocyanate or m-tetramethylxylenediisocyanate (m-TMXDI), or 1,5-diisocyanatonaphthalene (NDI).

In one embodiment, the diisocyanate is MDI.

Chain Extender

Herein at least one chain extender is included in the formation of thethermoplastic polyurethane or polyurethaneurea elastomer compositions. Achain extender is a compound that has two functional groups permolecule, such as diols or diamines, which are capable of reacting withan isocyanate group.

The chain extender may have a molecular weight range of 400 or less. Thechain extender may have a molecular weight range of about 800 to about1600. The chain extender may have a molecular weight range of about 400to about 4000.

The chain extender may be selected from diol or diamine chain extenders.In one embodiment at least one chain extender is a diol.

Examples of diol chain extenders include, but are not limited to:C₁₋₁₂alkane diols such as: 1,4-butanediol, 1,6-hexanediol,1,8-octanediol, 1,9-nonanediol and 1,10-decanediol, 1,4-cyclohexanedimethanol, p-xyleneglycol, 1,4-bis (2-hydroxyethoxy) benzene,1,12-dodecanediol and 1,3 bis-(4-hydroxybutyl)1,1,3,3-tetramethyldisiloxane.

In one embodiment at least one chain extender is a diamine. Suitablediamine chain extenders include C₁₋₁₂ alkane diamines such as1,2-ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,3bis-(3-aminopropyl) tetramethyldisiloxane, or 1,3 bis-(3-aminobutyl)tetramethyldisiloxane.

The wt % of a hard segment in a thermoplastic polyurethane orpolyurethaneurea (the wt % determined by the weight of a linkingcompound (for example a diisocyanate)+chain extender as a percentage ofthe total weight of the polyurethane/polyurethaneurea) may be in a rangeof about 20 wt % to about 60 wt %. Exemplified ranges include: about 30wt % to about 60 wt %, or about 40 wt % to about 60 wt %, about 50 wt %to about 60 wt % and about 40 wt % to about 50 wt %.

In one embodiment only one chain extender is used in the formation ofthe thermoplastic polyurethane or polyurethaneurea elastomercomposition.

In one embodiment two chain extenders are used in the formation of thethermoplastic polyurethane or polyurethaneurea elastomer composition.For example a combination of 1,4-butanediol and ethylene diamine.

Additional Polyol or Polyamine

Herein a thermoplastic polyurethane or polyurethaneurea elastomercompositions comprising a reaction product of: at least one blockcopolymer segment of Formula 1 as defined herein; a diisocyanate; andone or more chain extenders, may include an additional polyol orpolyamine.

The additional polyols may include poly(hexamethylene oxide),poly(heptamethylene oxide), poly(octamethylene oxide) (POMO),poly(decamethylene oxide) (PDMO), polydimethylsiloxane diols,poly(butadine diol), poly(carbonate) diol and poly(isobutylene)diol.

In one embodiment the additional polyol may be: a polydimethylsiloxanepolymer comprising at least two hydroxyl groups, for example α,ωbis-(6-hydroxyethoxypropyl)polydimethylsiloxane.

In one embodiment the additional polyol is a polyol of Formula J:

wherein:

-   -   R^(5a) and R^(6a) are each independently selected from a        straight chain, branched or cyclic, saturated and unsaturated        hydrocarbon radical optionally interrupted with one or more        heteroatoms independently selected from O, N and S; and    -   m′ is an integer of 1 to 50.

R^(5a) and R^(6a) may both be (CH₂)₂O(CH₂)₄.

In a another embodiment the additional polyol is a polyol of Formula K:

wherein:

X² is a group selected from: OC(O)O, C(O)O and O;

q′ is an integer of 1 to 50, including, for example, an integer of 5 to20; and

r′ is an integer of 1 to 50.

In one embodiment X² is O.

In a another embodiment the additional polyol is selected from:poly(hexamethylene oxide), poly(heptamethylene oxide),poly(octamethylene oxide) (POMO) and poly(decamethylene oxide) (PDMO).

The additional polyamines may include α,ωbis-(3-aminopropyl)polydimethylsiloxane, α,ωbis-(aminomethyl)polydimethylsiloxane, a,bis-(2-aminoethyl)polydimethylsiloxane, α,ωbis-(4-aminobutyl)polydimethylsiloxane, α,ωbis-(5-aminopentyl)polydimethylsiloxane and the like.

The additional polyamine may be a polyamine of Formula L:

wherein:

-   -   R^(5b) and R^(6b) are each independently selected from a        straight chain, branched or cyclic, saturated and unsaturated        hydrocarbon radical optionally interrupted with one or more        heteroatoms independently selected from O, N and S; and    -   m″ is an integer of 1 to 50.

R^(5b) and R^(6b) may both be (CH₂)₂O(CH₂)₄.

The additional polyamine may be a polyamine of Formula M:

wherein:

X³ is a group selected from: OC(O)O, C(O)O and O;

q″ is an integer of 1 to 50, including, for example, an integer of 5 to20; and

r″ is an integer of 1 to 50.

Processes for Preparing “Soft” Block Copolymers and Polyurethane orPolyurethaneurea Elastomer Compositions

Disclosed herein is a process for preparing a block copolymer segment ofFormula 1, whereby the process comprising the step of combining:

-   -   i. at least one macrodiol; or    -   ii. at least one macrodiamine; or    -   iii. a mixture of at least one macrodiol and at least one        macrodiamine, with a divalent linking compound.

Optional additional steps may include one or more of:

-   -   i. filtration;    -   ii. the removal of solvent(s), for example via evaporation under        reduced pressure; and/or    -   iii. purification, for example by distillation (such as        distillation via the use of Kugelrohr distillation apparatus).

Herein divalent linking compounds are compounds that can link twocomponents, such as two macrodiols or two macrodiamines, whereby thedivalent compound is at the nexus between the two components. A divalentlinking compound can create: urethane, urea, carbonate, amide, ester,and phosphonate linkages within the block copolymer segment.

Examples of divalent linking compounds are organophosphorus compounds orcompounds comprising two functional groups, such as two: isocyanate,carboxylic acid and acid halide functional groups.

In one embodiment the divalent linking compound is a diisocyanate, forexample: 1,4-diisocyanatobutane, 1,12-diisocyanatododecane,1,6-diisocyantehexane, 1,8-diisocyanateoctane, 4,4′-methylenediphenyldiisocyanate (MDI), 4,4′-methylenebis(cyclohexyl diisocyanate) (H12MDI),p-phenylene diisocyanate (p-PDI), m-phenylene diisocyanate (m-PDI)trans-cyclohexane-1,4-diisocyanate (CHDI) or a mixture of the cis andtrans isomers, 1,6-hexamethylene diisocyanate (HDI), 2,4-toluenediisocyanate (2,4-TDI) or its isomers (for example 2,6-toluenediisocyanate (2,6-TDI)), or mixtures thereof, p-tetramethylxylenediisocyanate (p-TMXDI), isophorone diisocyanate or m-tetramethylxylenediisocyanate (m-TMXDI), or 1,5-diisocyanatonaphthalene (NDI).

In another embodiment the divalent linking compound is an acid halide,for example phosgene.

In another embodiment the divalent compound is an organophosphoruscompound, for example methylphosphonic dichloride.

Also disclosed herein is a process for preparing a thermoplasticpolyurethane or polyurethaneurea elastomer comprising the silicon basedblock copolymer segment of Formula 1, whereby the process comprises thesteps of:

-   -   i. providing a block copolymer segment of Formula 1 or preparing        a block copolymer segment of Formula 1 using a process as        described herein;    -   ii. optionally further reacting the composition of step i. with        a divalent compound and: at least one macrodiol; at least one        macrodiamine; or a mixture of at least one macrodiol and at        least one macrodiamine; and    -   iii. reacting the block copolymer segment of step i. or ii. with        a chain extender or a mixture of chain extenders to form the        polyurethane or polyurethaneurea elastomer.

Non-limiting examples of soft segments which could be produced for thethermoplastic polyurethane or polyurethaneurea elastomeric compositionsdisclosed herein are shown in Schemes 1 to 4. In these schemes R^(5a)and R^(6a) are both (CH₂)₂O(CH₂)₄:

-   -   Scheme 1—The preparation of a linked macrodiol from        poly(hexamethylene oxide) (PHMO) using 4,4′-methylenediphenyl        diisocyanate (MDI) as the linker molecule.    -   Scheme 2—The preparation of a linked macrodiol from α,ω        bis-(6-hydroxyethoxypropyl)polydimethylsiloxane using MDI as the        linker molecule.    -   Scheme 3—The preparation of a linked macrodiol from        α,ω-bis-(6-hydroxyethoxypropyl)polydimethylsiloxane using a        carbonate linker:    -   Scheme 4—The preparation of a linked macrodiol from        α,ω-bis-(6-hydroxyethoxypropyl)polydimethylsiloxane using a        phosphonate linker.

As a non-limiting example, Scheme 5 illustrates a possible reactionscheme and the general structure of the polyurethane urea prepared fromMDI linked PHMO and PDMS chain extended with ethylene diamine.

Materials, Devices and Articles

Disclosed herein are materials that comprise a thermoplasticpolyurethane or polyurethaneurea elastomer composition as definedherein.

The thermoplastic polyurethane or polyurethaneurea elastomercompositions may be used to produce sheets of fabrics or fibres,especially for applications where materials possessing high tensilestrength and/or tear strength are required. For example thethermoplastic polyurethane or polyurethaneurea elastomer compositionscan be used to produce fibres that may be used in knitting or weavingspecialty fabrics, for example high strength and/or water-repellentmembranes. In addition, the thermoplastic polyurethane orpolyurethaneurea elastomer compositions may be used as sealants. Forcompositions comprising a siloxane component, due to the dielectricproperties of said siloxane component, the thermoplastic polyurethane orpolyurethaneurea elastomer compositions may be used for electronic andelectrical components and insulation.

Also disclosed herein are devices or articles which are composed whollyor partly of a thermoplastic polyurethane or polyurethaneurea elastomercomposition as defined herein.

Examples of devices or articles include: artificial leather, shoe soles,cable sheathing, varnishes, coatings, structural components for pumps orvehicles, mining ore screens, conveyor belts, laminating compounds,fibres, textiles, separation membranes, sealants, and adhesivecomponents.

Medical Devices, Articles or Implants

The thermoplastic polyurethane or polyurethaneurea elastomericcompositions defined herein may be used as biomaterials. Herein, theterm “biomaterial” is used in its broadest sense and refers to amaterial which is used in situations where it comes into contact withthe cells and/or bodily fluids of living animals or humans.

Disclosed herein are medical devices, articles or implants which arecomposed wholly or partly of a thermoplastic polyurethane orpolyurethaneurea elastomeric composition as defined herein.

Examples of medical devices, articles and implants include: a cardiacpacemaker, defibrillator, catheter, heart valve, cardiac assist device,vascular graft, implantable prosthesis, a cannula, extra-corporealdevice, artificial organ, pacemaker lead, defibrillator lead, bloodpump, balloon pump, A-V shunt, biosensor, membrane for cellencapsulation, drug delivery device, wound dressing, artificial joint,orthopaedic implant, or soft tissue replacement.

In one embodiment the medical device, article or implant is forcardiovascular applications, for example a device, article or implantthat relates to one or more of the aortic, mitral, pulmonary, and/ortricuspid valves.

In another embodiment the device may be a heart valve, or similar thatcan be inserted by a procedure called TAVI (Transcatheter Aortic ValveReplacement).

An example of an implantable valve 100 (for surgical and/or TAVIplacement) is presented in FIG. 1. The valve includes a plurality ofvalve leaflets 110-1, 110-2, and 110-3 constructed from the subjectpolymers. Each of leaflets 110 can be discrete from the others (asshown) or can be portions of one unitary (monolithic) leaflet body.Support structure for the valve may include an annular base portion 102that can have a planar or flat upstream terminus or can have a curved orscalloped upstream terminus (not shown) or extensions 104 that projectfrom annular base portion 102 downstream relative to intended flow. Theleaflets can be integrally formed on this base frame 102, such asthrough a casting (for example dip casting) or moulding process. In anexample of a dip casting process, the base frame 102 is placed on amandrel and dipped in a polymer, which results in the formation ofleaflets integrated with a polymeric coating over the base frame. Insome embodiments, leaflets 110 (formed of the subject polymers) can bephysically joined to support structure 102 through a coupling processsuch as sewing.

Herein, the thermoplastic polyurethane or polyurethaneurea elastomericcompositions used in the production of a medical device, article orimplant should be acceptable for use on or in a recipient, such as ahuman being. For example, the thermoplastic polyurethane orpolyurethaneurea elastomeric composition, should be able to contacttissues of a recipient without excessive toxicity, irritation, allergicresponse or other potential complications commensurate with a reasonablebenefit/risk ratio identified by a skilled medical professional orveterinarian.

It will be appreciated that in some cases thermoplastic polyurethane orpolyurethaneurea elastomeric compositions as described herein may not befor use on or in a recipient, such as a human being, but can be usefulin the preparation of thermoplastic polyurethane or polyurethaneureaelastomeric compositions which could be utilised in the preparation ofmaterials which are acceptable for use in medical devices, articles andimplants.

The recipients of medical devices, articles and implants describedherein can be human beings, male or female.

Alternatively the recipients of medical devices, articles and implantsdescribed herein can be a non-human animal. “Non-human animals” or“non-human animal” is directed to the kingdom Animalia, excludinghumans, and includes both vertebrates and invertebrates, male or female,and comprises: warm blooded animals, including mammals (comprising butnot limited to primates, dogs, cats, cattle, pigs, sheep, goats, rats,guinea pigs, horses, or other bovine, ovine, equine, canine, feline,rodent or murine species), birds, insects, reptiles, fish andamphibians.

The recipients of the medical devices, articles and implants describedherein are referred herein with the interchangeable terms “patient”,“recipient” “individual”, and “subject”. These four terms are usedinterchangeably and refer to any human or non-human animal (unlessindicated otherwise), as defined herein.

Examples Raw Materials

Certain chemicals referred to within the specification, including thefollowing examples, can be obtained from the suppliers indicted in Table2.

TABLE 2 Suppliers for selected compounds disclosed in the examples.Component Example Supplier α,ω Bis-(6- Shin-Etsuhydroxyethoxypropyl)polydimethylsiloxane (molecular weight 928)Hydrogenated poly(butadiene) diol Kraysol ® from Cray Valley4,4′-methylene diphenyl diisocyanate BASF 1,4-Butanediol Aldrich 1,3bis-(3-aminopropyl) Shin-Etsu tetramethyldisiloxane1,1,3,3-Bis-hydroxybutyl tetramethyl Shin-Etsu disiloxane

Equipment

Gel Permeation Chromatography: Waters THF System

Gel permeation chromatography (GPC) was performed on a Waters Alliancesystem equipped with an Alliance 2695 Separations Module (integratedquaternary solvent delivery, solvent degasser and autosampler system), aWaters column heater module, a Waters 2414 RDI refractive indexdetector, a Waters PDA 2996 photodiode array detector (210 to 400 nm at1.2 nm) and 4× Agilent PL-Gel columns (3×PL-Gel Mixed C (5 m) and1×PL-Gel Mixed E (3 m) columns), each 300 mm×7.8 mm², providing aneffective molar mass range of 10 to 4×10⁵). Tetrahydrofuran (THF) highpurity solvent (HPLC grade) was pre-filtered through aluminium oxide (90active neutral, 70-230 mesh) with 0.45 m filter, and 0.1 g L¹2,6-di-tert-butyl-4-methylphenol (BHT) was added as inhibitor. Thefiltered THF containing BHT was purged slowly with nitrogen gas and usedas an eluent with a flow rate of 1 mL/min at 30° C. Number (M_(n)) andweight average (M_(w)) molar masses were evaluated using WatersEmpower-3 software. The GPC columns were calibrated with low dispersitypolystyrene (PSt) standards (Polymer Laboratories) ranging from 265 to2,560,000 g mol⁻¹, and molar masses are reported as PSt equivalents. A3rd-order polynomial was used to fit the log M_(p) vs. time calibrationcurve, which was near linear across the molar mass ranges.

Gel Permeation Chromatography: Shimadzu—DMAc

Gel permeation chromatography (GPC) was performed on a Shimadzu systemequipped with a CMB-20A controller system, an SIL-20A HT autosampler, anLC-20AT tandem pump system, a DGU-20A degasser unit, a CTO-20AC columnoven, an RDI-10A refractive index detector, and 4× Waters Styragelcolumns (HT2, HT3, HT4, and HT5, each 300 mm×7.8 mm², providing aneffective molar mass range of 100-4×10⁶). N,N-Dimethylacetamide (DMAc)(containing 4.34 g L⁻¹ lithium bromide (LiBr)) was used as an eluentwith a flow rate of 1 mL/min at 80° C. Number (M_(n)) and weight average(M_(w)) molar masses were evaluated using Shimadzu LC Solution software.The GPC columns were calibrated with low dispersity polystyrene (PSt)standards (Polymer Laboratories) ranging from 575 to 3,242,000 g mol⁻¹,and molar masses are reported as PSt equivalents. A 3rd-order polynomialwas used to fit the log M_(p) vs. time calibration curve, which was nearlinear across the molar mass ranges

Film Preparation by Solvent Casting and Testing of Mechanical Properties

Polymer films of 80 mm×145 mm size were prepared by placing a solutionof the polymer in a Teflon mould and then evaporating the solvent slowlyin a nitrogen circulating oven at 60° C. for few hours followed byfurther drying under a vacuum (1 torr) overnight. The films were thenequilibrated at room temperature for at least 24 hours before using themfor tensile property measurement.

Dumbbell shaped specimens of polymer film were punched using a die and amanual cutting Press (IDM Instruments). The specimens had dimensions of75 mm length, 13 mm width at each end and 4 mm at the central narrowsection (constant width over at least 15 mm of length). Thickness of thecut out specimen was measured using a digital thickness gauge (Mitutoyo,Japan). In case there was small variation in thickness over the lengthof 15 mm in the central narrow section, an average of three thicknessvalues was taken. Instron 5565 fitted with static load cell ±100 N wasinitialized and the load was calibrated using Instron Bluehill 2(version 2.35) software. For the tensile test at dry condition, thespecimen was fixed between upper and lower grips (Instron) such that thegap between the grips was 10 mm. The 10 mm long section of the film wasstretched at the rate of 50 mm per minute until the film broke. At leastthree replicates of specimen were tested for each film. In case of widediscrepancy between results, five tests were carried out. Stress,strain, breaking stress and elongation at breaking were obtained fromthe software. These parameters allow one to obtain values for thetensile strength, the Young's modulus (stiffness) and Elongation(elasticity) of the samples.

For the tensile test at wet condition, (or replication of conditionsfound in medical applications) the cut out specimen of known thicknesswas put in a plastic bag and immersed in water maintained at 37° C. forat least two hours. The specimen was quickly dried using tissue paperand fixed between the grips and stretched at the rate of 100 mm per minuntil the film broke. Stress, strain, breaking stress and elongation atbreaking were obtained from the software. The stress values were plottedagainst strain (% of initial value).

Abbreviated Terms

Table 3 lists a series of abbreviated terms which are used herein.

TABLE 3 Acronyms used for compounds and components described hereinAcronym Compound/Component BAPD 1,3 Bis-(3-aminopropyl)tetramethyldisiloxane DMAc N′N-Dimethylacetamide GPC Gel PermeationChromatography MDI 4,4′-Methylenediphenyldiisocyanate M_(n) NumberAverage Molecular Weight M_(w) Weight Average Molecular Weight PDIPolydispersity Index PDMS α,ωBis-(6-hydroxyethoxypropyl)polydimethylsiloxane PHMO Poly(hexamethyleneoxide) PU Polyurethane PUU Polyurethaneurea EDA 1,2-ethanediamine BDO1,4-butanediol BHTD 1,1,3,3-bis-hydroxybutyltetramethylene disiloxane

Example 1—Synthesis of Urethane Linked Poly(Hexamethylene Oxide)(PHMO-u-PHMO)

Poly(hexamethylene oxide) (PHMO) (molecular weight 696.23) was preparedaccording to a method described in:

-   -   P. A. Gunatillake, G. F. Meijs, R. C. Chatellier, D. M. McIntosh        and E. Rizzardo, Polym. Int., 7, 275-283, 1992; and    -   U.S. Pat. No. 5,403,912.        The PHMO was dried and degassed by heating at 105° C. for about        15 hours under vacuum (0.1 torr) until the moisture content was        below 200 ppm, as determined by Karl Fisher titration. All        glassware used were dried overnight at 105° C. prior to use in        the experiment. Accurately weighed molten        4,4′-methylenediphenyldiisocyanate (MDI) (7.18 g) was placed in        a round bottom flask equipped with: a mechanical stirrer,        addition funnel and a nitrogen inlet. The flask was then placed        in an oil batch at 80° C. Pre-dried PHMO (40.00 g) was weighed        and added to MDI with stirring over a period of 20 minutes. The        reaction mixture was further reacted for about 2 hours until all        the isocyanate was consumed. This was confirmed by the absence        of an IR absorption band at 2275 cm¹.

Characterisation data for the PHMO prior to and after linking is shownin

Table 4.

TABLE 4 Molecular Weight Characterisation Data for Example 1: SystemM_(n) M_(w) PDI PHMO - Before Linking 1333 1999 1.49 PHMO - AfterLinking 4322 7272 1.68 (Urethane)

The linked-PHMO was stored under nitrogen at ambient temperature untilfurther use.

Example 2—Synthesis of Urethane Linked α,ωBis-(6-hydroxyethoxypropyl)-polydimethylsiloxane (PDMS-u-PDMS)

α,ω Bis-(6-hydroxyethoxypropyl)polydimethylsiloxane (molecular weight928) was dried and degassed at 105° C. for about 15 hours until themoisture content was below 200 ppm as determined by Karl Fishertitration. All glassware used were dried overnight at 105° C. before usein the experiment. Accurately weighed molten MDI (6.74 g) was placed ina round bottom flask equipped with: a mechanical stirrer, additionfunnel and a nitrogen inlet. The flask was then placed in an oil batchat 80° C. Pre-dried PDMS (50.0 g) was weighed accurately and added toMDI with stirring over a period of 20 minutes. The reaction mixture wasfurther reacted with stirring at 80° C. for about 2 hours until all theisocyanate was consumed, which was confirmed by the absence of an IRabsorption band at 2275 cm¹.

Characterisation data for the PHMO prior to and after linking is shownin

Table 5.

TABLE 5 Molecular Weight Characterisation Data for Example 2: PDI SystemM_(n) M_(w) (=M_(w)/M_(n)) Siloxane - Before 1334 1475 1.30 LinkingSiloxane - After 5302 7468 1.40 Linking (Urethane)

The results showed that the linking reaction was successful. Followingthe reactions, the product was stored under nitrogen at ambienttemperature.

Example 3—Synthesis of the Carbonate Linked PDMS (PDMS-c-PDMS)

In a three-necked 1 L round bottomed flask equipped with: a silica geldrying tube, a 250 mL pressure compensating dropping funnel, athermometer, and a magnetic stirrer bar, were placed 200 ml of drytoluene and 49.48 g of a 20% solution of phosgene in toluene. The flaskwas cooled, whilst stirring, to 0° C. 23.62 g of pyridine was addeddropwise to the mixture from the dropping funnel. The addition was madeover a 15 minute period during which time the temperature was maintainedin the range 0-5° C. 270.82 g of α,ω-bis(hydroxyethoxypropyl)polydimethylsiloxane (molecular weight 928) was then added drop wise tothe mixture from the dropping funnel. The addition was made over a 1hour period during which time the temperature of the mixture rose to 15°C. after which the reaction mixture was maintained at 15° C. for 2hours. During this period pyridine hydrochloride precipitated out of thereaction mixture. The reaction mixture was filtered through celite toremove the pyridine hydrochloride. The toluene was removed by rotaryevaporator at 80° C. under a reduced pressure of 20 torr. The mixturewas transferred to a Kugelrohr distillation apparatus and stripped oflow molecular weight species at 150° C. under a reduced of 8×10⁻² torrto give 202 g of (PDMS-1000)-c-(PDMS-1000) as a colourless oil(molecular weight 1924).

Example 4—Synthesis of the Phosphate Linked PDMS (PDMS-p-PDMS)

In a 500 ml round bottomed flask equipped with a magnetic stirrer barwere placed 100 ml of dry ether, 69.82 g of α,ω-bis(hydroxyethoxypropyl)polydimethylsiloxane (molecular weight 928), and 7.61 g oftriethylamine. A solution of 23.62 g of methylphosphonic dichloride in50 ml of ether was added drop wise to the mixture from the droppingfunnel. During this period triethylamine hydrochloride precipitated outof the reaction mixture. The reaction was stirred for a further 3 daysat room temperature. The reaction mixture was filtered to remove thepyridine hydrochloride. The ether was removed by rotary evaporator at80° C. under a reduced pressure of 20 torr to give 72 g ofPDMS-1000-P(O)Me-PDMS as a colourless oil.

Example 5—Preparation of a Polyurethaneurea (PUU) Using LinkedPHMO-u-PHMO, PDMS, BAPD with 40 Hard Segment Percentage

Accurately weighed linked PHMO-u-PHMO (10.00 g) prepared according tothe method described in Example 1, and α,ω-bis(hydroxyethoxypropyl)polydimethylsiloxane (PDMS) (MW 973, 40.00 g) were mixed in a flask anddegassed at 80° C. under vacuum (0.1 torr) for 2 hours. MDI (22.94 g)was accurately weighed in to a round bottom flask equipped with: amechanical stirrer, addition funnel and a nitrogen inlet. The flask wasthen placed in an oil batch at 80° C. The mixture of PHMO-u-PHMO andPDMS was added slowly over period of 30 minutes using an addition funnelto with stirring to MDI in the flask. After the addition was over, thereaction mixture was heated at 80° C. for 2 hours with stirring undernitrogen. Anhydrous N′N-dimethylacetamide (DMAc, 500 mL) was then addedusing a syringe to the reaction mixture and stirred for 5 minutes untila clear solution is obtained. The solution was cooled in an ice bath to0° C. and 1,3 bis-(3-aminopropyl) tetramethyldisiloxane (BAPD, 10.40 g)dissolved in anhydrous DMAc (25 mL) was added dropwise to thepre-polymer solution in the flask with stirring. After the addition wasover, the polymer solution was heated to 90° C. for a period of 3 hoursand transferred into a Schott bottle.

The polymer solution, after allowing to degas, was cast as thin film bypouring on to a Teflon mould. The mould was placed in an oven under aslow stream of nitrogen at 60° C. for 6 hours to remove the solvent,followed by placing it under vacuum (0.1 torr) for a further 16 hours toremove any remaining solvent.

Characterisation data for the prepared polymer is shown in Table 6.

Example 6—Preparation of a Polyurethaneurea (PUU) Using LinkedPDMS-u-PDMS, PHMO, BAPD with 40 Hard Segment Percentage

Accurately weighed linked PDMS-u-PDMS (40.00 g) prepared according tothe method described in Example 2, and PHMO (MW 696, 10.00 g) were mixedin a flask and degassed at 80° C. under vacuum (0.1 torr) for 2 hours.MDI (21.19 g) was accurately weighed in to a round bottom flask equippedwith: a mechanical stirrer, addition funnel and a nitrogen inlet. Theflask was then placed in an oil batch at 80° C. The mixture ofPDMS-u-PDMS and PHMO was added slowly over period of 30 minutes using anaddition funnel to with stirring to MDI in the flask. After the additionwas over, the reaction mixture was heated at 80° C. for 2 hours withstirring under nitrogen. Anhydrous DMAc (500 ml) was then added using asyringe to the reaction mixture and then stirred for 5 minutes until aclear solution was obtained. The solution was cooled in an ice bath to0° C. and BAPD (12.14 g) dissolved in anhydrous DMAc (25 mL) was addeddropwise to the pre-polymer solution in the flask with stirring. Afterthe addition was over, the polymer solution was heated to 90° C. for aperiod of 3 hours and transferred into a Schott bottle.

The polymer solution, after allowing to degas, was cast as thin film bypouring on to Teflon mould. The mould was placed in an oven under a slowstream of nitrogen at 60° C. for 6 hours to remove the solvent, followedby placing the mould under vacuum (0.1 torr) for 16 hours to remove anyremaining solvent.

Characterisation data for the prepared polymer is shown in Table 6.

Example 7—Preparation of a Polyurethaneurea (PUU) Using LinkedPDMS-c-PDMS, PHMO, BAPD with 40 Hard Segment Percentage

Accurately weighed linked PDMS-c-PDMS (40.00 g) prepared according tothe method described in Example 2, and PHMO (molecular weight 696, 10.00g) were mixed in a flask and degassed at 80° C. under vacuum (0.1 torr)for 2 hours. MDI (21.42 g) was accurately weighed in to a round bottomflask equipped with: a mechanical stirrer, addition funnel and anitrogen inlet. The flask was then placed in an oil batch at 80° C. Themixture of PDMS-c-PDMS and PHMO was added slowly over period of 30minutes using an addition funnel to with stirring to MDI in the flask.After the addition was over, the reaction mixture was heated at 80° C.for 2 hours with stirring under nitrogen. Anhydrous DMAc (500 mL) wasthen added using a syringe to the reaction mixture and stirred for 5minutes until a clear solution was obtained. The solution was cooled inan ice bath to 0° C. and BAPD (11.91 g) dissolved in anhydrous DMAc (25mL) was added dropwise to the pre-polymer solution in the flask withstirring. After the addition was over, the polymer solution was heatedto 90° C. for a period of 3 hours and transferred into a Schott bottle.

The polymer solution, after allowing to degas, was cast as thin film bypouring on to Teflon mould. The mould was placed in an oven under a slowstream of nitrogen at 60° C. for 6 hours to remove DMAc, followed byunder vacuum (0.1 torr) for 16 hours to remove any remaining solvent.

Characterisation data for the prepared polymer is shown in Table 6.

Example 8—Preparation of a Polyurethaneurea (PUU) Using LinkedPDMS-u-PDMS and BAPD without PHMO with 40 Hard Segment Percentage

Accurately weighed linked PDMS (40.0 g) was degassed at 80° C. for 2hours under vacuum (0.1 torr). Molten MDI (15.88 g) was placed in athree necked flask equipped with: a mechanical stirrer, dropping funneland a nitrogen inlet. The flask was then placed in an oil bath at 70° C.The degassed macrodiol mixture (50 g) was added dropwise through theaddition funnel over a period of 30 minutes. After the addition wasover, the reaction mixture was heated at 80° C. for 2 hours withstirring under nitrogen. Anhydrous DMAc (500 mL) was then added througha syringe to the reaction mixture and stirred for 5 minutes until it wasa clear solution. The solution was then cooled in an ice bath to 0° C.and BAPD (10.79 g) mixed with anhydrous DMAc (50 mL) was added dropwiseinto the above solution. After the addition was over, the above polymersolution was heated to 90° C. for a period of 3 hours and transferredinto a Schott bottle. The polymer solution was then degassed at 60° C.in a nitrogen circulating oven and cast into a 0.5-mm thick film.

The polymer solution, after allowing to degas, was cast as thin film bypouring on to Teflon mould. The mould was placed in an oven under a slowstream of nitrogen at 60° C. for 6 hours to remove solvent. The mouldwas then placed under vacuum (0.1 torr) for 16 hours to remove anyremaining solvent.

Example 9—Preparation of a Polyurethaneurea (PUU) Using LinkedPDMS-c-PDMSO, BDO with 40 Hard Segment Percentage by One-Step BulkPolymerisation

A mixture of pre-dried linked PDMS-c-PDMS (20.0 g) and 1.4-butanediol(BDO) (2.85 g) was weighed in a PP beaker and degassed at 80° C. under avacuum of 0.1 torr for over an hour. The vacuum was released undernitrogen and dibutyltindilaurate (DBTL) catalyst 0.1 wt-% was added andstirred manually with the spatula. Molten MDI (10.49 g) was then addedto the reaction mixture at once and stirred rapidly using spatula untilviscous enough and then poured into Teflon tray and cured at 100° C. for18 hours. The polymer was then compression moulded into a film using hotpress at 180° C. for mechanical properties.

Example 10—Preparation of a Polyurethaneurea (PUU) Using LinkedPHMO-u-PHMO, PDMS, BAPD with 50 Hard Segment Percentage

A PUU was synthesised according procedure as described in Example 5. Thefollowing quantities of reagents were used:

-   -   linked PHMO-u-PHMO (10.0 g);    -   PDMS (40.0 g);    -   MDI (31.68 g); and    -   BAPD (18.32 g).

Characterisation data for the prepared PUU is shown in Table 6.

Example 11—Preparation of a Polyurethaneurea (PUU) Using LinkedPHMO-u-PHMO, PDMS, EDA with 50 Hard Segment Percentage

The PUU was synthesised according procedure as described in Example 5.The following quantities of reagents were used:

-   -   linked PHMO-u-PHMO (10.0 g);    -   PDMS (40.0 g);    -   MDI (42.94 g); and    -   EDA (7.06) g.

Characterisation data for the prepared PUU is shown in Table 6.

Example 12—Preparation of a Polyurethaneurea (PUU) Using LinkedPDMS-u-PDMS, PHMO, BAPD with 50 Hard Segment Percentage

A PUU was synthesised according to the procedure as described in Example5. The following quantities of reagents were used:

-   -   linked PDMS-u-PDMS (40.0 g);    -   PHMO (10.0 g);    -   MDI (29.39 g); and    -   BAPD (20.61 g).

Characterisation data for the prepared PUU is shown in Table 6.

Example 13—Preparation of a Polyurethaneurea (PUU) Using LinkedPHMO-u-PHMO, PDMS, BAPD:EDA (8:2) with 50 Hard Segment Percentage

A mixture of PDMS (40.0 g) and PHMO-u-PHMO (10.0 g) was degassed at 80°C. for 2 hours under vacuum (0.1 torr). Molten MDI (32.91 g) was placedin a three necked flask equipped with: a mechanical stirrer, droppingfunnel and a nitrogen inlet. The flask was then placed in an oil bath at70° C. The degassed macrodiol mixture (50 g) was added dropwise throughthe addition funnel over a period of 30 minutes. After the addition wasover, the reaction mixture was heated at 80° C. for 2 hours withstirring under nitrogen. Anhydrous DMAc (500 mL) was then added througha syringe to the reaction mixture and stirred for 5 minutes until it wasa clear solution. The solution was then cooled in an ice bath to 0° C.BAPD (16.11 g) mixed with ethylene diamine (0.97 g) dissolved inanhydrous DMAc (60 mL) was added dropwise into above solution. After theaddition was over, the above polymer solution was heated to 90° C. for aperiod of 3 hours and transferred into a Schott bottle. The polymersolution was then degassed at 60° C. in a nitrogen circulating oven andcast into a thin film as described in Example 5.

Characterisation data for the prepared PUU is shown in Table 6.

Example 14—Preparation of a Polyurethaneurea (PUU) Using LinkedPHMO-u-PHMO, PDMS, BHTD:EDA (6:4) with 45 Hard Segment Percentage

A mixture of PDMS (40.0 g) and PHMO-u-PHMO (10.0 g) was degassed at 80°C. for 2 hours under vacuum (0.1 torr). Molten MDI (28.65 g) was placedin a three necked flask equipped with: a mechanical stirrer, droppingfunnel and a nitrogen inlet. The flask was then placed in an oil bath at70° C. The degassed macrodiol mixture (50.0 g) was added through theaddition funnel over a period of 30 minutes. After the addition wasover, the reaction mixture was heated at 80° C. for 2 hours withstirring under nitrogen. 1,1,3,3-Bis-hydroxybutyltetramethylenedisiloxane (BHTD) (10.72 g) was then added to the reaction mixture andthe system was allowed to react for a further 2 hours. The reactionmixture was then cooled down to 0° C. and anhydrous DMAc (500 mL) wasthen added through a syringe to the reaction mixture and stirred for 5minutes until it was a clear solution. EDA (1.54 g) dissolved inanhydrous DMAc (60 mL) was added dropwise into above solution. After theaddition was over, the above polymer solution was heated to 90° C. for aperiod of 3 hours and then transferred into a Schott bottle. The polymersolution was then degassed at 60° C. in a nitrogen circulating oven andcast into a thin film as described in Example 5.

Characterisation data for the prepared PUU is shown in Table 6.

Example 15—Preparation of a Polyurethaneurea (PUU) Using LinkedPHMO-u-PHMO, PDMS, BHTD:EDA (4:6) with 45 Hard Segment Percentage

The PUU was synthesised according to the procedure described in Example14. The following quantities of reagents were used:

-   -   linked PHMO-u-PHMO (10.0 g);    -   PDMS (40.0 g);    -   MDI (30.42 g);    -   BHTD (7.93 g); and    -   EDA (2.57 g).

Characterisation data for the prepared PUU is shown in Table 6.

Example 16—Preparation of a Polyurethaneurea (PUU) Using LinkedPHMO-u-PHMO, PDMS, BDO:EDA (6:4) with 45 Hard Segment Percentage

The PUU was synthesised according to the procedure described in Example14. The following quantities of reagents were used:

linked PHMO-u-PHMO (10.0 g);

-   -   PDMS (40.0 g);    -   MDI (34.19 g);    -   BHTD (4.65 g); and    -   BDO (2.07 g).

Characterisation data for the prepared PUU is shown in Table 6.

Example 17—Preparation of a Polyurethaneurea (PUU) Using LinkedPDMS-u-PDMS, PHMO, BHTD:EDA (6:4) with 45 Hard Segment Percentage

The PUU was synthesised following procedure as described in Example 14.The amount of precursors used are as follows:

-   -   linked PHMO-u-PHMO (10.0 g);    -   PDMS (40.0 g);    -   MDI (26.92 g);    -   BHTD (12.23 g); and    -   EDA (1.76 g).

Characterisation data for the prepared PUU is shown in Table 6.

Example 18—Preparation of a Polyurethaneurea (PUU) Using LinkedPDMS-u-PDMS, PHMO-u-PHMO, BHTD:EDA (6:4) with 45 Hard Segment Percentage

The PUU was synthesised according to the procedure described in Example14. The following quantities of reagents were used:

-   -   linked PHMO-u-PHMO (10.0 g);    -   PDMS-u-PDMS (40.0 g);    -   MDI (26.02 g);    -   BHTD (13.02 g); and    -   EDA (1.87 g).

Characterisation data for the prepared PUU is shown in Table 6.

Example 19—Preparation of a Polyurethaneurea (PUU) Using LinkedPHMO-u-PHMO, PDMS, BHTD:EDA (50:50) with 45 Hard Segment WeightPercentage

The PUU was synthesised according to the procedure described in Example14. The following quantities of reagents were used:

-   -   linked PHMO-u-PHMO (20.0 g);    -   PDMS (80.0 g);    -   MDI (58.33 g);    -   BHTD (19.32 g); and    -   EDA (4.17 g).

Example 20—Preparation of a Polyurethaneurea (PUU) Using LinkedPHMO-u-PHMO, PDMS, BAPD with 40 Hard Segment Weight Percentage

The PUU was synthesised according to the procedure described in Example14. The following quantities of reagents were used:

-   -   linked PHMO-u-PHMO (10.0 g);    -   PDMS (40.0 g);    -   MDI (29.32 g); and    -   BAPD (4.02 g)

Example 21—Tensile Testing of the Materials Produced in Examples 5-7, 10& 12-20

Tensile testing was carried out using dumbbells punched from driedpolyurethaneurea films prepared in Examples 5 to 7, 10 and 12-20.Tensile testing was carried out on an Instron model 5565 UniversalTesting Machine. The results are summarised in Table 6. These resultsindicate that the polyurethaneurea polymers of the current inventiondemonstrate high tensile strength and high elongation compared topolyurethaneurea polymers in the prior art.

Tensile testing of films prepared in Examples 13, 17, 18 and 20 wascarried out on an Instron model 5565 Universal Testing Machine using theprocedure described under the heading “Equipment”.

Characterisation data for the prepared PUUs are shown in Table 6 andTable 7.

TABLE 6 The molecular weight and tensile properties of polyurethaneureasprepared as described in Examples 5-7, 10 and 12-20 -21measured atambient temperature. Ultimate Tensile Young's Elongation StrengthModulus at Break GPC Characterisation Data Example (MPa) (MPa) (%) Mn MwPDI 5 20.6 ± 2.5 11.20 ± 0.8  1871 ± 26 85762 192726 2.2 6 22.26 ± 1.7 16.6 ± 0.7 1361 ± 12 86486 208711 2.35 7  6.0 ± 0.8 20.7 ± 4.0  570 ± 2069106 214173 2.8 10 14.98 ± 6.3  16.6 ± 0.7 1361 ± 12 72816 142744 1.9412 20.6 ± 2.5 11.20 ± 0.8  1871 ± 26 85762 192726 2.2 13 28.47 ± 1.5 57.7 ± 2.6  830 ± 4.9 119896 351073 2.53 14 18.5 ± 3.2 21.6 ± 3.0 1170 ±13 143469 544021 2.73 15 36.8 ± 0.8 52.8 ± 0.5 1100 ± 30 129302 2727312.01 16 31.7 ± 0.3 66.2 ± 6.1  860 ± 84 82800 156265 1.83 17  26.6 ±13.4 39.28 ± 8.5   990 ± 36 123109 394717 2.65 18 36.7 ± 3.6 35.1 ± 1.81180 ± 11 104911 213576 1.95 19 34.0 ± 2.7 35.8 ± 2.1 1367 ± 42 89147253274 2.84 20 23.6 ± 2.4 67.97 ± 10.9  800 ± 12 87372 158008 1.73

TABLE 7 The tensile properties of polyurethaneureas prepared asdescribed in Examples 13, 17, 18, and 20 measured at 37° C. temperature.Ultimate Tensile Young's Modulus Elongation at Example Strength (MPa)(MPa) Break (%) 13 27.53 ± 2.8 29.44 ± 0.63 950 ± 3 17  22.96 ± 10.6437.09 ± 4.8   860 ± 25 18 30.55 ± 3.2 28.84 ± 0.59 1180 ± 11 20 23.06 ±2.3 56.49 ± 4.2  880 ± 5

The polyurethaneureas prepared according to the present inventionexhibit high tensile strength, low modulus and high elongation as shownin Table 6. In particular, the polyurethaneureas prepared according toExamples 15 and 16 had tensile strength exceeding 30 MPa with elongationat break over 1000%. This combination of properties is unique and farexceeded those reported in prior art. For example, the polyurethaneureasdisclosed in International Patent Application WO00/64971 had elongationsat break less than 500% for materials described in all Examples.

It will be appreciated by persons skilled in the art that numerousvariations and/or modifications may be made to the above-describedembodiments, without departing from the broad general scope of thepresent disclosure. For example, it will be appreciated that embodimentsmay be variously combined or separated without parting from theinvention and that the preferred features described herein areapplicable to all aspects of the invention described herein. The presentembodiments are, therefore, to be considered in all respects asillustrative and not restrictive.

1-20. (canceled)
 21. A polymer comprising a plurality of hard segments;a first plurality of soft segments comprising a linked macrodiol havinga structure of Formula 1; and a second plurality of soft segmentscomprising a polyol,

wherein A¹ is a hydroxyl group; A² is hydrogen or a hydroxyl group; eachY¹ and Y² independently comprises a polysiloxane macrodiol, polyethermacrodiol, polycarbonate macrodiol, polyester macrodiol, or apolyhydrocarbon macrodiol; each L¹ and L² is independently a firstdivalent linking group; the first divalent linking group is created froma first divalent linking compound; the first divalent linking compoundis a diisocyanate; n is an integer of 1 to 5; t is 0 to 5; and Q isrepresented by Formula A or Formula B:

wherein R¹, R², R³, and R⁴, are each independently selected fromhydrogen and an optionally substituted straight chain, branched orcyclic, saturated or unsaturated hydrocarbon radical; R⁵ and R⁶ are eachindependently selected from a straight chain, branched or cyclic,saturated or unsaturated hydrocarbon radical optionally interrupted withone or more heteroatoms independently selected from O, N and S; m is aninteger of 1 to 50; X is a group selected from OC(O)O, C(O)O and O; q isan integer of 1 to 50; and r is an integer of 2 to 50, provided that (i)Q is represented by Formula B where X is O, (ii) Y² is a polyethermacrodiol, or (iii) the second plurality of soft segments comprises apolyether macrodiol.
 22. The polymer of claim 21, wherein Q is


23. The polymer of claim 21, wherein the first divalent linking compoundis selected from 1,4-diisocyanatobutane, 1,12-diisocyanatododecane,1,6-diisocyantehexane, 1,8-diisocyanateoctane, 4,4′-methylenediphenyldiisocyanate (MDI), 4,4′-methylenebis(cyclohexyl diisocyanate) (H12MDI),p-phenylene diisocyanate (p-PDI), m-phenylene diisocyanate (m-PDI),trans-cyclohexane-1,4-diisocyanate (CHDI) or a mixture of the cis andtrans isomers, 1,6-hexamethylene diisocyanate (HDI), 2,4-toluenediisocyanate (2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI),p-tetramethylxylene diisocyanate (p-TMXDI), isophorone diisocyanate orm-tetramethylxylene diisocyanate (m-TMXDI), 1,6-diisocyanatohexane(DICH), 1,3-bis(1-isocyanato-1-methylethyl)benzene, and1,5-diisocyanatonaphthalene (NDI).
 24. The polymer of claim 21, whereinthe first divalent linking compound is MDI.
 25. The polymer of claim 21,wherein Q is represented by Formula B; X is O; and q is
 6. 26. Thepolymer of claim 21, wherein t is 0; Q is represented by Formula B; thefirst divalent linking compound is MDI; Y² is a polyether macrodiol. 27.The polymer of claim 21, wherein the linked macrodiol has a structure ofFormula 1B(i)(a):

wherein X and X¹ are O; v is an integer of 1 to 50; and w is an integerof 2 to
 50. 28. The polymer of claim 21, wherein the linked macrodiolhas the following structure:


29. The polymer of claim 21, wherein the polyol in the second pluralityof soft segments has the following structure:

wherein R^(5a) and R^(6a) are each independently selected from astraight chain, branched or cyclic, saturated or unsaturated hydrocarbonradical optionally interrupted with one or more heteroatomsindependently selected from O, N and S; and m′ is an integer of 1 to 50.30. The polymer of claim 21, wherein the linked macrodiol has thefollowing structure:

and the polyol in the second plurality of soft segments has thefollowing structure:

wherein R^(5a) and R^(6a) are each independently selected from astraight chain, branched or cyclic, saturated or unsaturated hydrocarbonradical optionally interrupted with one or more heteroatomsindependently selected from O, N and S; and m′ is an integer of 1 to 50.31. The polymer of claim 21, wherein the plurality of hard segmentscomprise a chain extender covalently linked to soft segments via asecond divalent linking group.
 32. The polymer of claim 31, wherein thefirst divalent linking group and the second divalent linking group arethe same.
 33. The polymer of claim 31, wherein the chain extender is aC₁₋₁₂ alkane diol or a C₁₋₁₂ alkane diamine.
 34. The polymer of claim31, wherein the chain extender is selected from 1,4-butanediol,1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol,1,4-cyclohexane dimethanol, p-xyleneglycol,1,4-bis(2-hydroxyethoxy)benzene, 1,12-dodecanediol,1,3-bis-(4-hydroxybutyl)-1,1,3,3-tetramethyldisiloxane,1,2-ethylenediamine, 1,3-propanediamine, 1,4-butanediamine,1,3-bis-(3-aminopropyl)tetramethyldisiloxane, and1,3-bis-(3-aminobutyl)-tetramethyldisiloxane.
 35. The polymer of claim31, wherein the chain extender comprises 1,3bis-(4-hydroxybutyl)-1,1,3,3-tetramethyldisiloxane.
 36. The polymer ofclaim 31, wherein the chain extender comprises 1,2-ethylenediamine. 37.The polymer of claim 31, wherein the chain extender comprises1,2-ethylenediamine and 1,3bis-(4-hydroxybutyl)-1,1,3,3-tetramethyldisiloxane covalently linked bya third divalent linking group.
 38. The polymer of claim 37, wherein thethird divalent linking group is created from a third divalent linkingcompound; and the third divalent linking compound is a diisocyanate. 39.The polymer of claim 38, wherein the third divalent linking compound isMDI.
 40. The polymer of claim 21, wherein Y² and the polyol are not thesame.
 41. The polymer of claim 21, wherein Y² is a polyether macrodiol.42. The polymer of claim 21, wherein the second plurality of softsegments comprises poly(hexamethylene oxide), poly(heptamethyleneoxide), poly(octamethylene oxide), poly(decamethylene oxide),polydimethylsiloxane diols, poly(butadine diol), poly(carbonate) diol,poly(isobutylene)diol, or α,ωbis-(6-hydroxyethoxypropyl)polydimethyl-siloxane.
 43. The polymer ofclaim 21, wherein Y² is poly(hexamethylene oxide); and the secondplurality of soft segments comprises poly(hexamethylene oxide),poly(heptamethylene oxide), poly(octamethylene oxide),poly(decamethylene oxide), polydimethylsiloxane diols, poly(butadinediol), poly(carbonate) diol, poly(isobutylene)diol, or α,ωbis-(6-hydroxyethoxypropyl)polydimethyl-siloxane.
 44. The polymer ofclaim 21, wherein t is 0; Q is poly(hexamethylene oxide); the firstdivalent linking compound is MDI; Y² is poly(hexamethylene oxide); thesecond plurality of soft segments comprises α,ωbis-(6-hydroxyethoxypropyl)polydimethyl-siloxane; the plurality of hardsegments comprise a chain extender covalently linked to soft segmentsvia a second divalent linking group; the second divalent linking groupis created from a second divalent linking compound; the second divalentlinking compound is MDI; the chain extender comprises1,2-ethylenediamine and 1,3bis-(4-hydroxybutyl)-1,1,3,3-tetramethyldisiloxane covalently linked bya third divalent linking group; the third divalent linking group iscreated from a third divalent linking compound; and the third divalentlinking compound is MDI.
 45. The polymer of claim 21, wherein thepolymer is not crosslinked.